Recycle content mixed esters and solvents

ABSTRACT

A mixed ester composition having a recycle content value is obtained by reacting a recycle content feedstock to make a recycle content mixed ester or by deducting from a recycle inventory a recycle content value applied to a mixed ester composition. At least a portion of the recycle content value in the feedstock or in an allotment obtained by a mixed ester manufacturer has its origin in recycled waste and/or pyrolysis of recycled waste and/or in thermal steam cracking of recycle content pyoil.

FIELD OF THE INVENTION

The invention relates to recycle content in ester compositions, inparticular to recycle content in ester compositions such as isobutylisobutyrate, isobutyl acetate, ethyl acetate, and/or ethyl isobutyrate,where such recycle content was obtained directly or indirectly fromeffluents generated from pyrolyzing recycled waste material andthermally cracking the resulting recycle pyoils or generating and usingthe pygas from the pyrolysis of the recycled waste material.

BACKGROUND OF THE INVENTION

Certain mixed esters, particularly isobutyl isobutyrate, isobutylacetate, ethyl acetate, and ethyl isobutyrate, may function as importantsolvents products in the production of various chemical components andproducts. These esters are generally used in numerous applications suchas pharmaceuticals, crop protection (pesticides and insecticides),surfactants and detergents, food processing, solvents, fuel additives,oil and gas treatments, hardeners for epoxy resins, catalysts forpolyurethanes, intermediates, plasticizers, corrosion inhibitors,synthetic resins, ion exchangers, textile assistants, dyes, solvents,neutralizing agents, biocides, vulcanization accelerators, and/oremulsifiers.

Solid waste materials, especially non-biodegradable recycled wastematerials, can negatively impact the environment when disposed of inlandfills after a single use. Thus, from an environmental standpoint, itis desirable to recycle as much waste material as possible. However,recycling waste materials can be challenging from an economicstandpoint.

While some waste materials are relatively easy and inexpensive torecycle, other waste materials require significant and expensiveprocessing in order to be reused. Further, different types of wastematerials often require different types of recycling processes.

To maximize recycling efficiency, it would be desirable for large-scaleproduction facilities to be able to process feedstocks having recyclecontent originating from a variety of recycled waste materials.Commercial facilities involved in the production of non-biodegradableproducts or products that find their ultimate destination in a landfillcould benefit greatly from using recycle content feedstocks.

Some recycling efforts involve complicated and detailed segregation ofrecycled waste streams, which contributes to the increased cost ofobtaining streams of recycled waste content. For example, conventionalmethanolysis technologies require a high purity stream of PET. Somedownstream products are also quite sensitive to the presence of dyes andinks on recycled waste products, and their pretreatment and removal alsocontributes to increased costs of feedstocks made from such recycledwastes. It would be desirable to establish a recycle content without thenecessity for sorting down to a single type of plastic or recycled wastematerial, or which can tolerate a variety of impurities in recycledwaste streams that flow through to a feedstock.

In some cases, it may be difficult to dedicate a product having arecycle content to a particular customer or downstream synthetic processfor making a derivate of the product, particularly if the recyclecontent product is a gas or difficult to isolate. As related to a gas,there is a lack of infrastructure to segregate and distribute adedicated portion of a gas made exclusively from a recycle contentfeedstock since the gas infrastructure is continuously fluid and oftencommingles gas streams from a variety of sources.

Further, it is recognized that some regions desire to move away fromsole dependence on natural gas, ethane, or propane as the sole sourcefor making raw materials products such as ethylene and propylene andtheir downstream derivatives, and alternative or supplemental feedstocksto crackers would be desirable.

It is also desirable to synthesize mixed esters using existing equipmentand processes and without the need to invest in additional and expensiveequipment in order to establish a recycle content in the manufacture ofthe chemical compound or polymer.

It is also desirable to continue sourcing a raw material for makingmixed esters from aldehydes and alcohols made from olefins obtained fromcracker facilities that may find themselves stranded as production froma natural gas field or petroleum becomes economically unattractive.

Further, it is desirable for manufacturers of mixed esters to not besolely dependent on obtaining credits to establish a recycle content inmixed esters and thereby provide the mixed esters manufacturer with avariety of choices to establish recycle content.

It would also be desirable for mixed ester manufacturers to be able todetermine the amount and timing of establishing recycle content. Themixed ester manufacturer, at certain times or for different batches, maydesire to establish more or less recycle content or no recycle content.The flexibility in this approach without the need to add significantassets is desirable.

SUMMARY OF THE INVENTION

There is now provided a method of processing a composition deriveddirectly or indirectly from pyrolysis of a recycled waste (“pr-AD”),said method comprising feeding said pr-AD to a reactor in which analcohol is made.

There is now provided a method of processing a composition deriveddirectly or indirectly from pyrolysis of a recycled waste (“pr-ROH”),said method comprising feeding said pr-ROH to a reactor in which a mixedester is made.

There is also provided a method of making recycle content alcoholcomposition (“r-ROH”), said method comprising subjecting an aldehydecomposition at least a portion of which is derived directly orindirectly from pyrolyzing a recycled waste (“pr-AD”) to a syntheticprocess to thereby produce an alcohol effluent comprising r-ROH.

There is also provided a method of making recycle content mixed estercomposition (“r-EC”), said method comprising reacting an alcoholcomposition at least a portion of which is derived directly orindirectly from pyrolyzing a recycled waste (“pr-ROH”) with an acid toproduce a mixed ester effluent comprising r-EC.

There is further provided a method of making an alcohol comprising:

-   -   a. an alcohol manufacturer obtaining an aldehyde composition        from a supplier and either:        -   i. from said supplier, also obtaining a pyrolysis recycle            content allotment or        -   ii. from any person or entity, obtaining a pyrolysis recycle            content allotment without a supply of an aldehyde            composition from said person or entity transferring said            pyrolysis recycle content allotment; and    -   b. depositing at least a portion of the pyrolysis recycle        content allotment obtained in step a(i) or step a(ii) into a        recycle inventory, and    -   c. making an alcohol composition from any aldehyde composition        obtained from any source.

There is further provided a method of making a mixed ester comprising:

-   -   a. a mixed ester manufacturer obtaining an alcohol composition        from a supplier and either:        -   i. from said supplier, also obtaining a pyrolysis recycle            content allotment or        -   ii. from any person or entity, obtaining a pyrolysis recycle            content allotment without a supply of an alcohol composition            from said person or entity transferring said pyrolysis            recycle content allotment; and    -   b. depositing at least a portion of the pyrolysis recycle        content allotment obtained in step a(i) or step a(ii) into a        recycle inventory, and    -   c. making a mixed ester composition from any alcohol composition        obtained from any source.

There is also provided a method of making an alcohol, said methodcomprising:

-   -   a. an alcohol manufacturer obtaining an aldehyde composition        from a supplier and either:        -   i. from said supplier, also obtaining a pyrolysis recycle            content allotment or        -   ii. from any person or entity, obtaining a pyrolysis recycle            content allotment without a supply of an aldehyde            composition from said person or entity transferring said            pyrolysis recycle content allotment; and    -   b. said alcohol manufacturer making an alcohol composition        (“ROH”) from any aldehyde composition obtained from any source;        and    -   c. either:        -   i. applying the pyrolysis recycle content allotment to OH            made by the supply of aldehyde obtained in step (a); or        -   ii. applying the pyrolysis recycle content allotment to EC            not made by the supply of aldehyde obtained in step (a), or        -   iii. depositing the pyrolysis recycle content allotment into            a recycle inventory from which is deducted recycle content            value applying at least a portion of said value to:            -   1. EC to thereby obtain r-EC, or            -   2. to a compound or composition other than EC, or            -   3. both;                whether or not the recycle content value is obtained                from a pyrolysis recycle content allotment obtained in                step a(i) or step a(ii).

There is also provided a method of making a mixed ester, said methodcomprising:

-   -   a. a mixed ester manufacturer obtaining an alcohol composition        from a supplier and either:        -   i. from said supplier, also obtaining a pyrolysis recycle            content allotment or        -   ii. from any person or entity, obtaining a pyrolysis recycle            content allotment without a supply of an alcohol composition            from said person or entity transferring said pyrolysis            recycle content allotment; and    -   b. said mixed ester manufacturer making a mixed ester        composition (“CE”) from any alcohol composition obtained from        any source; and    -   c. either:        -   i. applying the pyrolysis recycle content allotment to EC            made by the supply of alcohol obtained in step (a); or        -   ii. applying the pyrolysis recycle content allotment to EC            not made by the supply of alcohol obtained in step (a), or        -   iii. depositing the pyrolysis recycle content allotment into            a recycle inventory from which is deducted recycle content            value applying at least a portion of said value to:            -   1. EC to thereby obtain r-EC, or            -   2. to a compound or composition other than EC, or            -   3. both;                whether or not the recycle content value is obtained                from a pyrolysis recycle content allotment obtained in                step a(i) or step a(ii).

In another method, there is provided a method of making a recyclecontent mixed ester composition (“r-EC”), said method comprising:

-   -   a. reacting any alcohol composition in a synthetic process to        make a mixed ester composition (“EC”); and    -   b. applying a recycle content value to at least a portion of        said EC to thereby obtain a recycle content mixed ester        composition (“r-EC”); and    -   c. optionally, obtaining said recycle content value by deducting        at least a portion of said recycle content value from a recycle        inventory, further optionally said recycle inventory also        containing a pyrolysis recycle content allotment or a pyrolysis        recycle content allotment deposit having been made into the        recycle inventory prior to the deduction; and    -   d. optionally communicating to a third party that said r-EC has        recycle content or is obtained or derived from recycled waste.

There is also provided a method of changing a recycle content value in arecycle content mixed ester composition (“r-EC”), said methodcomprising:

-   -   a. either:        -   i. reacting a recycle content alcohol composition (“r-OH) to            make a recycle content mixed ester composition (“r-EC”)            having a first recycle content value (“first r-EC”); or        -   ii. possessing a recycle content mixed ester composition            (“r-EC”) having a first recycle content value (also a “first            r-EC”); and    -   b. transferring a recycle content value between a recycle        inventory and said first r-EC to obtain a second recycle content        mixed ester composition having a second recycle content value        that is different than the first recycle content value (“second        r-EC”), wherein said transferring optionally includes either:        -   i. deducting said recycle content value from said recycle            inventory and applying said recycle content value to said            first r-EC to obtain said second r-EC having a second            recycle content value that is higher than the first recycle            content value; or        -   ii. deducting said recycle content value from said first            r-EC and adding said deducted recycle content value to said            recycle inventory to obtain said second r-EC having a second            recycle content value that is lower than the first recycle            content value.

There is provided another method for making a recycle content mixedester composition (“r-EC”), said method comprising:

-   -   a. pyrolyzing a pyrolysis feed comprising a recycled waste        material to thereby form a pyrolysis effluent comprising recycle        pyoil (r-pyoil) and/or a recycle pygas (“r-pygas”);    -   b. optionally cracking a cracker feed comprising at least a        portion of the r-pyoil to thereby produce a cracker effluent        comprising r-olefins; or optionally cracking a cracker feed        without r-pyoil to make olefins and applying a recycle content        value to the olefins so made by deducting a recycle content        value from a recycle inventory and applying it to the olefins to        make r-olefins; and    -   c. reacting any olefin volume in a synthetic process to make an        aldehyde composition and/or an alcohol composition; and    -   d. optionally reacting at least a portion of any aldehyde        composition in a synthetic process to make said alcohol        composition; and    -   e. reacting at least a portion of any alcohol composition in a        synthetic process to make a mixed ester composition; and    -   f. applying a recycle content value to at least a portion said        mixed ester composition based on:        -   i. feeding a pyrolysis recycle content mixed ester            composition (“pr-EC”) as a feedstock or        -   ii. depositing at least a portion of an allotment obtained            from any one or more of steps a) or b) into a recycle            inventory and deducting from said inventory a recycle            content value and applying at least a portion of said value            to EC to thereby obtain r-EC.

There is also provided a direct method of making a recycle content mixedester (“r-EC”), said method comprising:

-   -   a. obtaining a recycle content alcohol composition at least a        portion of which is directly derived from cracking r-pyoil or        obtained from r-pygas (“dr-ROH”),    -   b. making a mixed ester composition from a feedstock comprising        the dr-ROH,    -   c. applying a recycle content value to at least a portion of any        mixed ester composition made by the same entity that made the        mixed ester composition in step b), wherein said recycle content        value is based at least partly on the amount of recycle content        contained in the dr-ROH.

There are a variety of uses provided. There is provided a use of recyclealdehyde composition derived directly or indirectly from pyrolyzing arecycled waste (“r-AD”) comprising converting the r-AD in a syntheticprocess to make an alcohol composition.

There are a variety of uses provided. There is provided a use of recyclealcohol composition derived directly or indirectly from pyrolyzing arecycled waste (“r-ROH”) comprising converting the r-ROH in a syntheticprocess to make a mixed ester composition.

There is also provided a use of a recycle inventory comprising:

-   -   a. converting any alcohol composition in a synthetic process to        make a mixed ester composition (“EC”); and    -   b. applying a recycle content value to said EC based at least        partly on a deduction from a recycle inventory, wherein at least        a portion of the inventory contains a recycle content allotment.

There is also provided an integrated method of making a recycle contentmixed ester composition (“r-EC”), said method comprising:

-   -   a. optionally providing an aldehyde manufacturing facility that        produces at least in part an aldehyde composition (“AD”);    -   b. providing an alcohol manufacturing facility that produces at        least in part an alcohol composition (“ROH”) and comprising a        reactor configured to accept AD;    -   c. providing a mixed ester manufacturing facility that makes a        mixed ester composition (“EC”) and comprising a reactor        configured to accept ROH; and    -   d. feeding at least a portion of said ROH from the alcohol        manufacturing facility to the mixed ester manufacturing facility        through a supply system providing fluid communication between        said facilities;        wherein any one or all of the aldehyde manufacturing facility,        alcohol manufacturing facility, or mixed ester manufacturing        facility makes or supplies a r-ROH or recycle content mixed        ester (r-EC), respectively, and optionally, wherein the alcohol        manufacturing facility supplies r-ROH to the mixed ester        manufacturing facility through said supply system.

There is provided another integrated system comprising:

-   -   a. an olefin manufacturing facility configured to produce an        output composition comprising a recycle content propylene or        recycle content ethylene or both (“r-olefin”);    -   b. an optional aldehyde manufacturing facility configured to        accept an olefin stream from the olefin manufacturing facility        and making an output composition comprising an aldehyde        composition;    -   c. an alcohol manufacturing facility configured to accept an        olefin stream from the olefin manufacturing facility and/or an        aldehyde stream from the aldehyde manufacturing facility and        making an output composition comprising an alcohol composition;    -   d. a mixed ester manufacturing facility having a reactor        configured to accept an alcohol composition and making an output        composition comprising a recycle content mixed ester (“r-EC);        and    -   e. a supply system providing fluid communication between at        least two of these facilities and capable of supplying the        output composition of one manufacturing facility to another of        the one or more manufacturing facilities.

There is further provided an integrated system comprising:

-   -   a. an olefin manufacturing facility configured to produce an        output composition comprising a recycle content propylene or        recycle content ethylene or both (“r-olefin”);    -   b. an optional aldehyde manufacturing facility configured to        accept an olefin stream from the olefin manufacturing facility        and making an output composition comprising an aldehyde        composition;    -   c. an alcohol manufacturing facility configured to accept an        olefin stream from the olefin manufacturing facility and/or an        aldehyde stream from the aldehyde manufacturing facility and        making an output composition comprising an alcohol composition;    -   d. a mixed ester manufacturing facility having a reactor        configured to accept an alcohol composition and make an output        composition comprising a recycle content mixed ester; and    -   e. a piping system interconnecting at least two of said        facilities, optionally with intermediate processing equipment or        storage facilities, capable of taking off the output composition        from one facility and accept said output at any one or more of        the other facilities.

There is further provided a system or package comprising:

-   -   a. a mixed ester, and    -   b. an identifier associated with said mixed ester, said        identifier being a representation that said mixed ester has        recycle content or is made from a source having recycle content.

There is also provided a method of offering to sell or selling a recyclemixed ester comprising:

-   -   a. converting an alcohol composition in a synthetic process to        make mixed ester composition (“EC”),    -   b. applying a recycle content value to at least a portion of the        EC to thereby obtain a recycle EC (“r-EC”), and    -   c. offering to sell or selling the r-EC as having a recycle        content or obtained or derived from recycled waste.

There are also provided recycle content mixed esters having a monomerderived from a r-AD composition, and any articles made from recyclecontent mixed esters.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is an illustrate of a process for employing a recycle contentpyrolysis oil composition (r-pyoil) to make one or more recycle contentcompositions into r-compositions.

FIG. 2 is an illustration of an exemplary pyrolysis system to at leastpartially convert one or more recycled waste, particularly recycledplastic waste, into various useful r-products.

FIG. 3 is a schematic depiction of pyrolysis treatment throughproduction of olefin containing products.

FIG. 4 is a block flow diagram illustrating steps associated with thecracking furnace and separation zones of a system for producing anr-composition obtained from cracking r-pyoil and non-recycle crackerfeed.

FIG. 5 is a schematic diagram of a cracker furnace suitable forreceiving r-pyoil.

FIG. 6 illustrates a furnace coil configuration having multiple tubes.

FIG. 7 illustrates a variety of feed locations for r-pyoil into acracker furnace.

FIG. 8 illustrates a cracker furnace having a vapor-liquid separator.

FIG. 9 is a block diagram illustrating the treatment of a recyclecontent furnace effluent.

FIG. 10 illustrates a fractionation scheme in a Separation section,including a demethanizer, dethanizer, depropanizer, and thefractionation columns to separate and isolate the main r-compositions,including r-propylene, r-ethylene, r-butylene, and others.

FIG. 11 illustrates the laboratory scale cracking unit design.

FIG. 12 illustrates design features of a plant-based trial feedingr-pyoil to a gas fed cracker furnace.

FIG. 13 is a graph of the boiling point curve of a r-pyoil having 74.86%C8+, 28.17% C15+, 5.91% aromatics, 59.72% paraffins, and 13.73%unidentified components by gas chromatography analysis.

FIG. 14 is a graph of the boiling point curve of a r-pyoil obtained bygas chromatography analysis.

FIG. 15 is a graph of the boiling point curve of a r-pyoil obtained bygas chromatography analysis.

FIG. 16 is a graph of the boiling point curve of a r-pyoil distilled ina lab and obtained by chromatography analysis.

FIG. 17 is a graph of the boiling point curve of r-pyoil distilled inlab with at least 90% boiling by 350° C., 50% boiling between 95° C. and200° C., and at least 10% boiling by 60° C.

FIG. 18 is a graph of the boiling point curve of r-pyoil distilled inlab with at least 90% boiling by 150° C., 50% boiling between 80° C. and145° C., and at least 10% boiling by 60° C.

FIG. 19 is a graph of the boiling point curve of r-pyoil distilled inlab with at least 90% boiling by 350° C., at least 10% by 150° C., and50% boiling between 220° C. and 280° C.

FIG. 20 is a graph of the boiling point curve of r-pyoil distilled inlab with 90% boiling between 250-300° C.

FIG. 21 is a graph of the boiling point curve of r-pyoil distilled inlab with 50% boiling between 60-80° C.

FIG. 22 is a graph of the boiling point curve of r-pyoil distilled inlab with 34.7% aromatic content.

FIG. 23 is a graph of the boiling point curve of r-pyoil used in theplant trial experiments.

FIG. 24 is a graph of the carbon distribution of the r-pyoil used in theplant experiments.

FIG. 25 is a graph of the carbon distribution by cumulative weightpercent of the r-pyoil used in the plant experiments.

DETAILED DESCRIPTION OF THE INVENTION

The word “containing” and “including” is synonymous with comprising.When a numerical sequence is indicated, it is to be understood that eachnumber is modified the same as the first number or last number in thenumerical sequence or in the sentence, e.g. each number is “at least,”or “up to” or “not more than” as the case may be; and each number is inan “or” relationship. For example, “at least 10, 20, 30, 40, 50, 75 wt.% . . . ” means the same as “at least 10 wt. %, or at least 20 wt. %, orat least 30 wt. %, or at least 40 wt. %, or at least 50 wt. %, or atleast 75 wt. %,” etc.; and “not more than 90 wt. %, 85, 70, 60 . . . ”means the same as “not more than 90 wt. %, or not more than 85 wt. %, ornot more than 70 wt. % . . . ” etc.; and “at least 1%, 2%, 3%, 4%, 5%,6%, 7%, 8%, 9% or 10% by weight . . . ” means the same as “at least 1wt. %, or at least 2 wt. %, or at least 3 wt. % . . . ” etc.; and “atleast 5, 10, 15, 20 and/or not more than 99, 95, 90 weight percent”means the same as “at least 5 wt. %, or at least 10 wt. %, or at least15 wt. % or at least 20 wt. % and/or not more than 99 wt. %, or not morethan 95 wt. %, or not more than 90 weight percent . . . ” etc.; or “atleast 500, 600, 750° C. . . . ” means the same as “at least 500° C., orat least 600° C., or at least 750° C. . . . ” etc.

All concentrations or amounts are by weight unless otherwise stated. An“olefin-containing effluent” is the furnace effluent obtained bycracking a cracker feed containing r-pyoil. A “non-recycleolefin-containing effluent” is the furnace effluent obtained by crackinga cracker feed that does not contain r-pyoil. Units on hydrocarbon massflow rate, MF1, and MF2 are in kilo pounds/hr (klb/hr), unless otherwisestated as a molar flow rate.

As used herein, “containing” and “including” are open ended andsynonymous with “comprising.”

The term “recycle content” is used herein i) as a noun to refer to aphysical component (e.g., compound, molecule, or atom) at least aportion of which is derived directly or indirectly from recycled wasteor ii) as an adjective modifying a particular composition (e.g., acompound, polymer, feedstock, product, or stream) at least a portion ofwhich is directly or indirectly derived from recycled waste.

As used herein, “recycle content composition,” “recycle composition,”and “r-composition” mean a composition having recycle content.

The term “pyrolysis recycle content” is used herein i) as a noun torefer to a physical component (e.g., compound, molecule, or atom) atleast a portion of which is derived directly or indirectly from thepyrolysis of recycled waste or ii) as an adjective modifying aparticular composition (e.g., a feedstock, product, or stream) at leasta portion of which is directly or indirectly derived from the pyrolysisof recycled waste. For example, pyrolysis recycle content can bedirectly or indirectly derived from recycle content pyrolysis oil,recycle content pyrolysis gas, or the cracking of recycle contentpyrolysis oil such as through thermal steam crackers or fluidizedcatalytic crackers.

As used herein, “pyrolysis recycle content composition,” “pyrolysisrecycle composition,” and “pr-composition” mean a composition (e.g., acompound, polymer, feedstock, product, or stream) having pyrolysisrecycle content. A pr-composition is a subset of a r-composition, whereat least a portion of the recycle content of the r-composition isderived directly or indirectly from the pyrolysis of recycled waste.

As used herein, a composition (e.g., compound, polymer, feedstock,product, or stream) “directly derived” or “derived directly” fromrecycled waste has at least one physical component that is traceable torecycled waste, while a composition (e.g., a compound, polymer,feedstock, product, or stream) “indirectly derived” or “derivedindirectly” from recycled waste has associated with it a recycle contentallotment and may or may not contain a physical component that istraceable to recycled waste.

As used herein, a composition (e.g., compound, polymer, feedstock,product, or stream) “directly derived” or “derived directly” from thepyrolysis of recycled waste has at least one physical component that istraceable to the pyrolysis of recycled waste, while a composition (e.g.,a compound, polymer, feedstock, product, or stream) “indirectly derived”or “derived indirectly” from the pyrolysis of recycled waste hasassociated with it a recycle content allotment and may or may notcontain a physical component that is traceable to the pyrolysis ofrecycled waste.

As used herein, “pyrolysis oil” or “pyoil” mean a composition of matterthat is liquid when measured at 25° C. and 1 atm and at least a portionof which is obtained from pyrolysis.

As used herein, “recycle content pyrolysis oil,” “recycle pyoil,”“pyrolysis recycle content pyrolysis oil” and “r-pyoil”mean pyoil, atleast a portion of which is obtained from pyrolysis, and having recyclecontent.

As used herein, “pyrolysis gas” and “pygas” mean a composition of matterthat is gas when measured at 25° C. and 1 atm and at least a portion ofwhich is obtained from pyrolysis.

As used herein, “recycle content pyrolysis gas,” “recycle pygas,”“pyrolysis content pyrolysis gas” and “r-pygas” mean pygas, at least aportion of which is obtained from pyrolysis, and having recycle content.

As used herein, “pyrolysis recycle content pyrolysis gas,” “pyrolysisrecycle pygas,” and “pr-pygas” mean r-pygas having pyrolysis recyclecontent.

As used herein, “AD” is an aldehyde composition (e.g., a feedstock,product, or stream).

As used herein, “recycle content aldehyde” and “r-AD” mean an AD havingrecycle content.

As used herein, “pyrolysis recycle content aldehyde” and “pr-AD” meanr-AD having pyrolysis recycle content.

As used herein, “ROH” is an alcohol composition (e.g., a feedstock,product, or stream).

As used herein, “recycle content alcohol” and “r-ROH” mean a ROH havingrecycle content.

As used herein, “pyrolysis recycle content alcohol” and “pr-ROH” meanr-ROH having pyrolysis recycle content.

As used herein, “EC” is a mixed ester composition (e.g., a feedstock,product, or stream).

As used herein, a “recycle content mixed ester” and “r-EC” mean EChaving recycle content.

As used throughout, the generic description of the compound, compositionor stream does not require the presence of its species, but also doesnot exclude and may include its species. For example, an “EC” or “anyEC” can include a mixed ester made by any process and may or may notcontain recycle content and may or may not be made from a non-recyclecontent feedstocks or from recycle content feedstocks, and may or maynot include r-EC or pr-EC. Likewise, r-EC may or may not include pr-EC,although the mention of r-EC does require it to have recycle content. Inanother example, an “AD” or “any AD” can include an aldehyde made by anyprocess and may or may not have recycle content, and may or may notinclude r-AD or pr-AD. Likewise, r-AD may or may not include pr-AD,although the mention of r-AD does require it to have recycle content.

As used herein, a “pyrolysis content mixed ester” and “pr-EC” mean r-EChaving pyrolysis recycle content.

As used herein, “Et” is ethylene composition (e.g., a feedstock,product, or stream) and “Pr” is propylene composition (e.g., afeedstock, product, or stream).

As used herein, “recycle content ethylene,” “r-ethylene” and “r-Et” meanEt having recycle content; and “recycle content propylene,”“r-propylene” and “r-Pr” mean Pr having recycle content.

As used herein, “pyrolysis recycle content ethylene” and “pr-Et” meanr-Et having pyrolysis recycle content; and “pyrolysis recycle contentpropylene” and “pr-Pr” mean r-Pr having pyrolysis recycle content.

As used herein, “EO” is ethylene oxide composition (e.g., a feedstock,product, or stream).

As used herein, a “recycle content ethylene oxide” and “r-EO” mean EOhaving recycle content.

As used herein, a “pyrolysis content ethylene oxide” and “pr-EO” meanr-EO having pyrolysis recycle content.

As used throughout, the generic description of the compound, compositionor stream does not require the presence of its species, but also doesnot exclude and may include its species. For example, an “EC” or “anyEC” can include mixed ester made by any process and may or may notcontain recycle content and may or may not be made from non-recyclecontent feedstocks or from recycle content feedstocks, and may or maynot include r-EC or pr-EC. Likewise, r-EC may or may not include pr-EC,although the mention of r-EC does require it to have recycle content. Inanother example, an “AD” or “any AD” can include ethylene made by anyprocess and may or may not have recycle content, and may or may notinclude r-AD or pr-DD. Likewise, r-AD may or may not include pr-AD,although the mention of r-AD does require it to have recycle content.

“Pyrolysis recycle content” is a specific subset/type (species) of“recycle content” (genus). Wherever “recycle content” and “r-” are usedherein, such usage should be construed as expressly disclosing andproviding claim support for “pyrolysis recycle content” and “pr-,” evenif not expressly so stated. For example, whenever the term “recyclecontent mixed ester” or “r-EC” is used herein, it should be construed asalso expressly disclosing and providing claim support for “pyrolysisrecycle content mixed ester” and “pr-EC.”

As used throughout, whenever a cracking of r-pyoil is mentioned, suchcracking can be conducted by a thermal cracker, or a thermal steamcracker, in a liquids fed furnace, or in a gas fed furnace, or in anycracking process. In one embodiment or in combination with any of thementioned embodiments, the cracking is not catalytic or is conducted inthe absence of an added catalyst or is not a fluidized catalyticcracking process.

As used throughout, whenever mention is made of pyrolysis of recyclewaste, or r-pyoil, all embodiments also include (i) the option ofcracking the effluent of pyrolyzing recycle waste or cracking r-pyoiland/or (ii) the option of cracking the effluent or r-pyoil as a feed toa gas fed furnace or to the tubes of gas furnace/cracker.

As used throughout, a “Family of Entities” means at least one person orentity that directly or indirectly controls, is controlled by, or isunder common control with another person or entity, where control meansownership of at least 50% of the voting shares, or shared management,common use of facilities, equipment, and employees, or family interest.As used throughout, the mention of a person or entity provides claimsupport for and includes any person or entity among the Family ofEntities.

In an embodiment or in combination with any other mentioned embodiments,the mention of r-AD also includes pr-AD, or pr-AD obtained directly orindirectly from the cracking of r-pyoil or obtained from r-pygas; r-ROHalso includes pr-ROH, or pr-ROH, and r-AD also includes pr-AD, or pr-ADobtained directly or indirectly from the cracking of r-pyoil or obtainedfrom r-pygas.

In one embodiment or in combination with any of the mentionedembodiments, there is provided a method for making a r-AC composition byreacting an AD with an acid in the presence of a catalyst. The ROH canbe a r-Et or a pr-Et or a dr-Et. In one embodiment, the method formaking a r-EC starts with feeding r-ROH to a reactor for making EC.

FIG. 1 is a schematic depiction illustrating an embodiment or incombination with any embodiment mentioned herein of a process foremploying a recycle content pyrolysis oil composition (r-pyoil) (orrecycled waste) to make one or more recycle content compositions (e.g.ethylene, propylene, butadiene, hydrogen, and/or pyrolysis gasoline):the r-composition.

As shown in FIG. 1 , recycled waste can be subjected to pyrolysis inpyrolysis unit 10 to produce a pyrolysis product/effluent comprising arecycle content pyrolysis oil composition (r-pyoil). The r-pyoil can befed to a cracker 20, along with a non-recycle cracker feed (e.g.,propone, ethane, and/or natural gasoline). A recycle content crackedeffluent (r-cracked effluent) can be produced from the cracker and thensubjected to separation in a separation train 30. In an embodiment or incombination with any embodiment mentioned herein or in combination withany of the mentioned embodiments, the r-composition can be separated andrecovered from the r-cracked effluent. The r-propylene stream cancontain predominantly propylene, while the r-ethylene stream can containpredominately ethylene.

As used herein, a furnace includes the convection zone and the radiantzone. A convection zone includes the tubes and/or coils inside theconvection box that can also continue outside the convection boxdownstream of the coil inlet at the entrance to the convection box. Forexample, as shown in FIG. 5 , the convection zone 310 includes the coilsand tubes inside the convection box 312 and can optionally extend or beinterconnected with piping 314 outside the convection box 312 andreturning inside the convection box 312. The radiant zone 320 includesradiant coils/tubes 324 and burners 326. The convection zone 310 andradiant zone 320 can be contained in a single unitary box, or inseparate discrete boxes. The convection box 312 does not necessarilyhave to be a separate discrete box. As shown in FIG. 5 , the convectionbox 312 is integrated with the firebox 322.

Unless otherwise specified, all component amounts provided herein (e.g.for feeds, feedstocks, streams, compositions, and products) areexpressed on a dry basis.

As used herein, a “r-pyoil” or “r-pyrolysis oil” are interchangeable andmean a composition of matter that is liquid when measured at 25° C. and1 atm, at least a portion of which is obtained from pyrolysis, and whichhas recycle content. In one embodiment or in combination with any of thementioned embodiments, at least a portion of the composition is obtainedfrom the pyrolysis of recycled waste (e.g., waste plastic or wastestream).

In one embodiment or in combination with any of the mentionedembodiments, the “r-ethylene” can be a composition comprising: (a)ethylene obtained from cracking of a cracker feed containing r-pyoil, or(b) ethylene having a recycle content value attributed to at least aportion of the ethylene; and the “r-propylene” can be a compositioncomprising (a) propylene obtained from cracking of a cracker feedcontaining r-pyoil, or (b) propylene having a recycle content valueattributed to at least a portion of the propylene.

Reference to a “r-ethylene molecule” means ethylene molecule deriveddirectly or indirectly from recycled waste and reference to a“pr-ethylene molecule” means ethylene molecule derived directly orindirectly from r-pyrolysis effluent (e.g., r-pyoil and/or r-pygas).

As used herein, a “Site” means a largest continuous geographicalboundary owned by a mixed ester manufacturer, or by one person orentity, or combination of persons or entities, among its Family ofEntities, wherein the geographical boundary contains one or moremanufacturing facilities at least one of which is mixed estermanufacturing facility.

As used herein, the term “predominantly” means more than 50 percent byweight, unless expressed in mole percent, in which case it means morethan 50 mole %. For example, a predominantly propane stream,composition, feedstock, or product is a stream, composition, feedstock,or product that contains more than 50 weight percent propane, or ifexpressed as mole %, means a product that contains more than 50 mole %propane.

As used herein, a composition that is “directly derived” from crackingr-pyoil has at least one physical component that is traceable to anr-composition at least a portion of which is obtained by or with thecracking of r-pyoil, while a composition that is “indirectly derived”from cracking r-pyoil has associated with it a recycle content allotmentand may or may not contain a physical component that is traceable to anr-composition at least a portion of which is obtained by or with thecracking of r-pyoil.

As used herein, “recycle content value” and “r-value” mean a unit ofmeasure representative of a quantity of material having its origin inrecycled waste. The r-value can have its origin in any type of recycledwaste processed in any type of process.

As used herein, the term “pyrolysis recycle content value” and“pr-value” mean a unit of measure representative of a quantity ofmaterial having its origin in the pyrolysis of recycled waste. Thepr-value is a specific subset/type of r-value that is tied to thepyrolysis of recycled waste. Therefore, the term r-value encompasses,but does not require, a pr-value.

The particular recycle content value (r-value or pr-value) can be bymass or percentage or any other unit of measure and can be determinedaccording to a standard system for tracking, allocating, and/orcrediting recycle content among various compositions. A recycle contentvalue can be deducted from a recycle content inventory and applied to aproduct or composition to attribute recycle content to the product orcomposition. A recycle content value does not have to originate frommaking or cracking r-pyoil unless so stated. In one embodiment or incombination with any mentioned embodiments, at least a portion of ther-pyoil from which an allotment is obtained is also cracked in acracking furnace as described throughout the one or more embodimentsherein.

In one embodiment or in combination with any mentioned embodiments, atleast a portion of the recycle content allotment or allotment or recyclecontent value deposited into a recycle content inventory is obtainedfrom r-pyoil. Desirably, at least 60%, or at least 70%, or at least 80%,or at least 90% or at least 95%, or up to 100% of the:

-   -   a. allotments or    -   b. deposits into a recycle content inventory, or    -   c. recycle content value in a recycle content inventory, or    -   d. recycle content value applied to compositions to make a        recycle content product, intermediate, or article (Recycle PIA)    -   are obtained from r-pyoil.

A Recycle PIA or r-PIA is a product, intermediate or article which caninclude compounds or compositions containing compounds or polymers,and/or an article having an associated recycle content value. A PIA doesnot have a recycle content value associated with it. A PIA includes, andis not limited to, ethylene oxide, or an alkylene glycol such asethylene glycol.

As used herein, “recycle content allotment” or “allotment” means arecycle content value that is:

-   -   a. transferred from an originating composition (e.g., compound,        polymer, feedstock, product, or stream) at least a portion of        which is obtained from recycled waste or which has a recycle        content value at least a portion of which originates from        recycled waste, optionally originating from r-pyoil, to a        receiving composition (the composition receiving the allotment,        e.g., compound, polymer, feedstock, product, or stream) that may        or may not have a physical component that is traceable to a        composition at least a portion of which is obtained from        recycled waste; or    -   b. deposited into a recycle inventory from an originating        composition (e.g., compound, polymer, feedstock, product, or        stream) at least a portion of which is obtained from or having a        recycle content value or pr-value at least a portion of which        originates from recycled waste.

As used herein, “pyrolysis recycle content allotment” and “pyrolysisallotment” or “pr-allotment” mean a pyrolysis recycle content value thatis:

-   -   a. transferred from an originating composition (e.g., compound,        polymer, feedstock, product, or stream) at least a portion of        which is obtained from the pyrolysis of recycled waste or which        has a recycle content value at least a portion of which        originates from the pyrolysis of recycled waste, to a receiving        composition (e.g., compound, polymer, feedstock, product,        article or stream) that may or may not have a physical component        that is traceable to a composition at least a portion of which        is obtained from the pyrolysis of recycled waste; or    -   b. deposited into a recycle inventory from an originating        composition (e.g., compound, polymer, feedstock, product, or        stream) at least a portion of which is obtained from or having a        recycle content value at least a portion of which originates        from the pyrolysis of recycled waste.

A pyrolysis recycle content allotment is a specific type of recyclecontent allotment that is tied to the pyrolysis of recycled waste.Therefore, the term recycle content allotment encompasses pyrolysisrecycle content allocation.

In one embodiment or in combination with any of the mentionedembodiments, a pyrolysis recycle content allotment or pyrolysisallotment may have a recycle content value that is:

-   -   a. transferred from an originating composition (e.g., compound,        polymer, feedstock, product, or stream) at least a portion of        which is obtained from the cracking (e.g. liquid or gas thermal        stream cracking) of r-pyoil, or transferred from recycle waste        used to make r-pyoil that is cracked, or transferred from        r-pyoil that is or will be cracked, or which has a recycle        content value at least a portion of which originates from the        cracking (e.g. liquid or gas thermal steam cracking) of r-pyoil,        to a receiving composition (e.g., compound, polymer, feedstock,        product, or stream or PIA) that may or may not have a physical        component that is traceable to a composition at least a portion        of which is obtained from the cracking of r-pyoil; or    -   b. deposited into a recycle content inventory and is obtained        from a composition (e.g., compound, polymer, feedstock, product,        or stream) at least a portion of which is obtained from or        having a recycle content value at least a portion of which        originates from the cracking (e.g. liquid or gas thermal steam        cracking) of r-pyoil (whether or not the r-pyoil is cracked at        the time of depositing the allotment into the recycle content        inventory provided the r-pyoil from which the allotment is taken        is ultimately cracked).

An allotment can be an allocation or a credit.

A recycle content allotment can include a recycle content allocation ora recycle content credit obtained with the transfer or use of a rawmaterial. In one embodiment or in combination with any of the mentionedembodiments, the composition receiving the recycle content allotment canbe a non-recycle composition, to thereby convert the non-recyclecomposition to an r-composition.

As used herein, “non-recycle” means a composition (e.g., compound,polymer, feedstock, product, or stream) none of which was directly orindirectly derived from recycled waste.

As used herein, a “non-recycle feed” in the context of a feed to thecracker or furnace means a feed that is not obtained from a recycledwaste stream. Once a non-recycle feed obtains a recycle contentallotment (e.g. either through a recycle content credit or recyclecontent allocation), the non-recycle feed become a recycle content feed,composition, or Recycle PIA.

As used herein, the term “recycle content allocation” is a type ofrecycle content allotment, where the entity or person supplying acomposition sells or transfers the composition to the receiving personor entity, and the person or entity that made the composition has anallotment at least a portion of which can be associated with thecomposition sold or transferred by the supplying person or entity to thereceiving person or entity. The supplying entity or person can becontrolled by the same entity or person(s), or Family of Entities, or adifferent Family of Entities. In one embodiment or in combination withany mentioned embodiments, a recycle content allocation travels with acomposition and with the downstream derivates of the composition. In oneembodiment or in combination with any mentioned embodiments, anallocation may be deposited into a recycle content inventory andwithdrawn from the recycle content inventory as an allocation andapplied to a composition to make an r-composition or a Recycle PIA.

As used herein, “recycle content credit” and “credit” mean a type ofrecycle content allotment, where the allotment is not restricted to anassociation with compositions made from cracking r-pyoil or theirdownstream derivatives, but rather have the flexibility of beingobtained from r-pyoil and (i) applied to compositions or PIA made fromprocesses other than cracking feedstocks in a furnace, or (ii) appliedto downstream derivatives of compositions, through one or moreintermediate feedstocks, where such compositions are made from processesother than cracking feedstocks in a furnace, or (iii) available for saleor transfer to persons or entities other than the owner of theallotment, or (iv) available for sale or transfer by other than thesupplier of the composition that is transferred to the receiving entityor person. For example, an allotment can be a credit when the allotmentis taken from r-pyoil and applied by the owner of the allotment to a BTXcomposition, or cuts thereof, made by said owner or within its Family ofEntities, obtained by refining and fractionation of petroleum ratherthan obtained by cracker effluent products; or it can be a credit if theowner of the allotment sells the allotment to a third party to allow thethird party to either re-sell the product or apply the credit to one ormore of a third party's compositions.

A credit can be available for sale or transfer or use, or can be sold ortransferred or used, either:

-   -   a. without the sale of a composition, or    -   b. with the sale or transfer of a composition but the allotment        is not associated with the sale or transfer of the composition,        or    -   c. is deposited into or withdrawn from a recycle content        inventory that does not track the molecules of a recycle content        feedstock to the molecules of the resulting compositions which        were made with the recycle content feedstocks, or which does        have such tracking capability but which did not track the        particular allotment as applied to a composition.

In one embodiment or in combination with any of the mentionedembodiments, an allotment may be deposited into a recycle contentinventory, and a credit or allocation may be withdrawn from theinventory and applied to a composition. This would be the case where anallotment is created by making a first composition from the pyrolysis ofrecycle waste, or from r-pyoil or the cracking of r-pyoil, or by anyother method of making a first composition from recycle waste,depositing the allocation associated with such first composition into arecycle content inventory, and deducting a recycle content value fromthe recycle content inventory and applying it to a second compositionthat is not a derivate of the first composition or that was not actuallymade by the first composition as a feedstock. In this system, one neednot trace the source of a reactant back to the cracking of pyoil or backto any atoms contained in olefin-containing effluent, but rather can useany reactant made by any process and have associated with such reactanta recycle content allotment.

In one embodiment or in combination with any mentioned embodiments, acomposition receiving an allotment is used as a feedstock to makedownstream derivatives of the composition, and such composition is aproduct of cracking a cracker feedstock in a cracker furnace. In oneembodiment or in combination with any mentioned embodiments, there isprovided a process in which:

-   -   a. a r-pyoil is obtained,    -   b. a recycle content value (or allotment) is obtained from the        r-pyoil and        -   i. deposited into a recycle content inventory, and an            allotment (or credit) is withdrawn from the recycle content            inventory and applied to any composition to obtain a            r-composition, or        -   ii. applied directly to any composition, without depositing            into a recycle content inventory, to obtain an            r-composition; and    -   c. at least a portion of the r-pyoil is cracked in a cracker        furnace, optionally according to any of the designs or processes        described herein; and    -   d. optionally at least a portion of the composition in step b.        originates from a cracking a cracker feedstock in a cracker        furnace, optionally the composition having been obtained by any        of the feedstocks, including r-pyoil, and methods described        herein.

The steps b. and c. do not have to occur simultaneously. In oneembodiment or in combination with any mentioned embodiments, they occurwithin a year of each other, or within six (6) months of each other, orwithin three (3) months of each other, or within one (1) month of eachother, or within two (2) weeks of each other, or within one (1) week ofeach other, or within three (3) days of each other. The process allowsfor a time lapse between the time an entity or person receiving ther-pyoil and creating the allotment (which can occur upon receipt orownership of the r-pyoil or deposit into inventory) and the actualprocessing of the r-pyoil in a cracker furnace.

As used herein, “recycle content inventory” and “inventory” mean a groupor collection of allotments (allocations or credits) from which depositsand deductions of allotments in any units can be tracked. The inventorycan be in any form (electronic or paper), using any or multiple softwareprograms, or using a variety of modules or applications that together asa whole tracks the deposits and deductions. Desirably, the total amountof recycle content withdrawn (or applied to compositions) does notexceed the total amount of recycle content allotments on deposit in therecycle content inventory (from any source, not only from cracking ofr-pyoil). However, if a deficit of recycle content value is realized,the recycle content inventory is rebalanced to achieve a zero orpositive recycle content value available. The timing for rebalancing canbe either determined and managed in accordance with the rules of aparticular system of accreditation adopted by the olefin-containingeffluent manufacturer or by one among its Family of Entities, oralternatively, is rebalanced within one (1) year, or within six (6)months, or within three (3) months, or within one (1) month of realizingthe deficit. The timing for depositing an allotment into the recyclecontent inventory, applying an allotment (or credit) to a composition tomake a r-composition, and cracking r-pyoil, need not be simultaneous orin any particular order. In one embodiment or in combination with anymentioned embodiments, the step of cracking a particular volume ofr-pyoil occurs after the recycle content value or allotment from thatvolume of r-pyoil is deposited into a recycle content inventory.Further, the allotments or recycle content values withdrawn from therecycle content inventory need not be traceable to r-pyoil or crackingr-pyoil, but rather can be obtained from any waste recycle stream, andfrom any method of processing the recycle waste stream. Desirably, atleast a portion of the recycle content value in the recycle contentinventory is obtained from r-pyoil, and optionally at least a portion ofr-pyoil, are processed in the one or more cracking processes asdescribed herein, optionally within a year of each other and optionallyat least a portion of the volume of r-pyoil from which a recycle contentvalue is deposited into the recycle content inventory is also processedby any or more of the cracking processes described herein.

The determination of whether a r-composition is derived directly orindirectly from recycled waste is not on the basis of whetherintermediate steps or entities do or do not exist in the supply chain,but rather whether at least a portion of the r-composition that is fedto the reactor for making an end product such as EO or AD can be tracedto an r-composition made from recycled waste.

The determination of whether a pr-composition is derived directly orindirectly from the pyrolysis of recycled waste (e.g., from the crackingof r-pyoil or from r-pygas) is not on the basis of whether intermediatesteps or entities do or do not exist in the supply chain, but ratherwhether at least a portion of the pr-composition that is fed to thereactor for making an end product such as EU can be traced to apr-composition made from the pyrolysis of recycled waste.

As noted above, the end product is considered to be directly derivedfrom cracking r-pyoil or from recycled waste if at least a portion ofthe reactant feedstock used to make the product can be traced back,optionally through one or more intermediate steps or entities, to atleast a portion of the atoms or molecules that make up an r-compositionproduced from recycled waste or the cracking of r-pyoil fed to acracking furnace or as an effluent from the cracking furnace).

The r-composition as an effluent may be in crude form that requiresrefining to isolate the particular r-composition. The r-compositionmanufacturer can, typically after refining and/or purification andcompression to produce the desired grade of the particularr-composition, sell such r-composition to an intermediary entity whothen sells the r-composition, or one or more derivatives thereof, toanother intermediary for making an intermediate product or directly tothe product manufacturer. Any number of intermediaries and intermediatederivates can be made before the final product is made.

The actual r-composition volume, whether condensed as a liquid,supercritical, or stored as a gas, can remain at the facility where itis made, or can be shipped to a different location, or held at anoff-site storage facility before utilized by the intermediary or productmanufacturer. For purposes of tracing, once an r-composition made fromrecycled waste (e.g., by cracking r-pyoil or from r-pygas) is mixed withanother volume of the composition (e.g. r-ethylene mixed withnon-recycle ethylene), for example in a storage tank, salt dome, orcavern, then the entire tank, dome, or cavern at that point becomes ar-composition source, and for purposes of tracing, withdrawal from suchstorage facility is withdrawing from an r-composition source until suchtime as when the entire volume or inventory of the storage facility isturned over or withdrawn and/or replaced with non-recycle compositionsafter the r-composition feed to the tank stops. Likewise, this appliesalso to any downstream storage facilities for storing the derivatives ofthe r-compositions, such as r-EC, r-ROH, r-AD, pr-AD, r-Et and pr-Etcompositions.

An r-composition is considered to be indirectly derived from recycledwaste or pyrolysis of recycled waste or cracking of r-pyoil if it hasassociated with it a recycle content allotment and may or may notcontain a physical component that is traceable to an r-composition atleast a portion of which is obtained from recycled waste/pyrolysis ofrecycled waste/cracking of r-pyoil. For example, the (i) manufacturer ofthe product can operate within a legal framework, or an associationframework, or an industry recognized framework for making a claim to arecycle content through, for example, a system of credits transferred tothe product manufacturer regardless of where or from whom ther-composition, or derivatives thereof, or reactant feedstocks to makethe product, is purchased or transferred, or (ii) a supplier of ther-composition or a derivate thereof (“supplier”) operates within anallotment framework that allows for associating or applying a recyclecontent value or pr-value to a portion or all of an olefin-containingeffluent or a compound within an olefin-containing effluent or derivatethereof to make an r-composition, and to transfer the recycle contentvalue or allotment to the manufacturer of the product or anyintermediary who obtains a supply of r-composition from the supplier. Inthis system, one need not trace the source of r-AD and/or r-ROH volumeback to the manufacture of r-composition or its derivatives fromrecycled waste/pyrolyzed recycled waste, but rather can use any aldehydecomposition made by any process and have associated with such aldehydecomposition a recycle content allotment.

Examples of how an AD composition for making ROH and EC can obtainrecycle content include:

-   -   (i) a cracker facility in which the propylene and/or r-ethylene        is made at the facility, by cracking r-pyoil or obtained from        r-pygas, can be in fluid communication, continuously or        intermittently and directly or indirectly through intermediate        facilities such as an AD facility, with an AD formation facility        (which can be to a storage vessel at the AD facility or directly        to the AD formation reactor) through interconnected pipes,        optionally through one or more storage vessels and valves or        interlocks, and the r-propylene and/or r-ethylene feedstock is        drawn through the interconnected piping:        -   a. from the cracker facility while r-propylene and/or            r-ethylene is being made or thereafter within the time for            the r-propylene and/or r-ethylene to transport through the            piping to the AD formation facility; or        -   b. from the one or more storage tanks at any time provided            that at least one of the storage tanks was fed with            r-propylene and/or r-ethylene, and continue for so long as            the entire volume of the one or more storage tanks is            replaced with a feed that does not contain r-propylene            and/or r-ethylene; or    -   (ii) transporting propylene and/or ethylene from a storage        vessel, dome, or facility, or in an isotainer via truck or rail        or ship or a means other than piping, that contains or has been        fed with r-propylene and/or r-ethylene until such time as the        entire volume of the vessel, dome or facility has been replaced        with an propylene and/or ethylene feed that does not contain        r-propylene and/or r-ethylene; or    -   (iii) the manufacturer of the AD certifies, represents to its        customers or the public, or advertises that its AD contains        recycle content or is obtained from feedstock containing or        obtained from recycle content, where such recycle content claim        is based in whole or in part on obtaining r-propylene and/or        r-ethylene feedstock associated with an allocation from        r-propylene and/or r-ethylene made from cracking r-pyoil or        obtained from r-pygas); or    -   (iv) the manufacturer of the AD has acquired:        -   a. an propylene and/or ethylene volume made from r-pyoil            under a certification, representation, or as advertised, or        -   b. has transferred credits or allocation with the supply of            propylene and/or ethylene to the manufacturer of the AD            sufficient to allow the manufacturer of the AD to satisfy            the certification requirements or to make its            representations or advertisements, or        -   c. an propylene and/or ethylene that has an associated            recycle content value where such recycle content value was            obtained, through one or more intermediary independent            entities, from a cracked r-propylene and/or            r-ethylene/r-pyoil or ethylene volume at least part of which            is obtained cracking r-pyoil or obtained from r-pygas.

As discussed above, the recycle content can be a pyrolysis recyclecontent that is directly or indirectly derived from the pyrolysis ofrecycled waste (e.g., from cracking r-pyoil or from r-pygas).

In one embodiment or in combination with any mentioned embodiments,there is provided a variety of methods for apportioning the recyclecontent among the various olefin-containing effluent volumes, orcompounds thereof, made by any one entity or a combination of entitiesamong the Family of Entities olefin-containing effluent. For example,the cracker furnace owner or operator olefin-containing effluent, or anyamong its Family of Entities, or a Site, can:

-   -   a. adopt a symmetric distribution of recycle content values        among at least two compounds within the olefin-containing        effluent or among PIA it makes based on the same fractional        percentage of recycle content in one or more feedstocks or based        on the amount of allotment received. For example, if 5 wt. % of        the entire cracker feedstock to a furnace is r-pyoil, then one        or more of the compounds in the olefin-containing effluent may        contain 5 wt. % recycle content value, or one or more compounds        can contain 5 wt. % recycle content value less any yield losses,        or one or more of the PIA can contain a 5% recycle content        value. In this case, the amount of recycle content in the        compounds is proportional to all the other products receiving        the recycle content value; or b. adopt an asymmetric        distribution of recycle content values among the compounds in        the olefin-containing effluent or among its PIA. In this case,        the recycle content value associated with a compound or PIA on a        can exceed the recycle content value associated with other        compounds or PIA. For example, one volume or batch of        olefin-containing effluent can receive a greater amount of        recycle content value that other batches or volume of        olefin-containing effluent, or one or a combination of compounds        among the olefin-containing effluent to receive a        disproportionately higher amount of recycle content value        relative to the other compounds in the olefin-containing        effluent or other PIA, some of which may receive no recycle        content value. One volume of olefin-containing effluent or PIA        can contain 20% recycle content by mass, and another volume or        PIA can contain zero 0% recycle content, even though both        volumes may be compositionally the same and continuously        produced, provided that the amount of recycle content value        withdrawn from a recycle content inventory and applied to the        olefin-containing effluent does not exceed the amount of recycle        content value deposited into the recycle content inventory, or        if a deficit is realized, the overdraft is rebalanced to zero or        a positive credit available status as described above, or if no        recycle content inventory exists, then provided that total        amount of recycle content value associated with any one or more        compounds in the olefin-containing effluent does not exceed the        allotment obtained from the r-pyoil or it is exceeded, is then        rebalanced. In the asymmetric distribution of recycle content, a        manufacturer can tailor the recycle content to volumes of        olefin-containing effluent or to the compounds of interest in        the olefin-containing effluent or PIA that are sold as needed        among customers, thereby providing flexibility among customers        some of whom may need more recycle content than others in an        r-compound or Recycle PIA.

In an embodiment or in combination with any embodiment mentioned herein,both the symmetric distribution and the asymmetric distribution ofrecycle content can be proportional on a Site wide basis, or on amulti-Site basis. In one embodiment or in combination with any of thementioned embodiments, the recycle content obtained from r-pyoil can bewithin a Site, and recycle content values from the r-pyoil can beapplied to one or more olefin-containing effluent volumes or one or morecompounds in a volume of olefin-containing effluent or to one or morePIA made at the same Site from compounds in an olefin-containingeffluent. The recycle content values can be applied symmetrically orasymmetrically to one or more different olefin-containing effluentvolumes or one or more compounds within an olefin-containing effluent orPIA made at the Site.

In one embodiment or in combination with any of the mentionedembodiments, the recycle content input or creation (recycle contentfeedstock or allotments) can be to or at a first Site, and recyclecontent values from said inputs are transferred to a second Site andapplied to one or more compositions made at a second Site. The recyclecontent values can be applied symmetrically or asymmetrically to thecompositions at the second Site.

A recycle content value that is directly or indirectly “derived fromcracking r-pyoil”, or a recycle content value that is “obtained fromcracking r-pyoil” or originating in cracking r-pyoil does not imply thetiming of when the recycle content value or allotment is taken,captured, deposited into a recycle content inventory, or transferred.The timing of depositing the allotment or recycle content value into arecycle content inventory, or realizing, recognizing, capturing, ortransferring it, is flexible and can occur as early as receipt ofr-pyoil onto the site within a Family of Entities, possessing it, orbringing the r-pyoil into inventory by the entity or person, or withinthe Family of Entities, owning or operating the cracker facility. Thus,an allotment or recycle content value on a volume of r-pyoil can beobtained, captured, deposited into a recycle content inventory, ortransferred to a product without having yet fed that volume to crackerfurnace and cracked. The allotment can also be obtained during feedingr-pyoil to a cracker, during cracking, or when an r-composition is made.An allotment taken when r-pyoil is owned, possessed, or received anddeposited into a recycle content inventory is an allotment that isassociated with, obtained from, or originates from cracking r-pyoil eventhough, at the time of taking or depositing the allotment, the r-pyoilhas not yet been cracked, provided that the r-pyoil is at some futurepoint in time cracked.

In an embodiment or in combination with any mentioned embodiments, ther-composition, or downstream reaction products thereof, or Recycle PIA,has associated with it, or contains, or is labelled, advertised, orcertified as containing recycle content in an amount of at least 0.01wt. %, or at least 0.05 wt. %, or at least 0.1 wt. %, or at least 0.5wt. %, or at least 0.75 wt. %, or at least 1 wt. %, or at least 1.25 wt.%, or at least 1.5 wt. %, or at least 1.75 wt. %, or at least 2 wt. %,or at least 2.25 wt. %, or at least 2.5 wt. %, or at least 2.75 wt. %,or at least 3 wt. %, or at least 3.5 wt. %, or at least 4 wt. %, or atleast 4.5 wt. %, or at least 5 wt. %, or at least 6 wt. %, or at least 7wt. %, or at least 10 wt. %, or at least 15 wt. %, or at least 20 wt. %,or at least 25 wt. %, or at least 30 wt. %, or at least 35 wt. %, or atleast 40 wt. %, or at least 45 wt. %, or at least 50 wt. %, or at least55 wt. %, or at least 60 wt. %, or at least 65 wt. % and/or the amountcan be up to 100 wt. %, or up to 95 wt. %, or up to 90 wt. %, or up to80 wt. %, or up to 70 wt. %, or up to 60 wt. %, or up to 50 wt. %, or upto 40 wt. %, or up to 30 wt. %, or up to 25 wt. %, or up to 22 wt. %, orup to 20 wt. %, or up to 18 wt. %, or up to 16 wt. %, or up to 15 wt. %,or up to 14 wt. %, or up to 13 wt. %, or up to 11 wt. %, or up to 10 wt.%, or up to 8 wt. %, or up to 6 wt. %, or up to 5 wt. %, or up to 4 wt.%, or up to 3 wt. %, or up to 2 wt. %, or up to 1 wt. %, or up to 0.9wt. %, or up to 0.8 wt. %, or up to 0.7 wt. %. The recycle content valueassociated with the r-composition, r-compounds or downstream reactionproducts thereof can be associated by applying an allotment (credit orallocation) to any composition, compound, or PIA made or sold. Theallotment can be contained in an inventory of allotments created,maintained or operated by or for the Recycle PIA or r-compositionmanufacturer. The allotment can be obtained from any source along anymanufacturing chain of products provided that its origin is in crackinga feedstock containing r-pyoil.

In one embodiment or in combination with any mentioned embodiments, theRecycle PIA manufacturer can make a Recycle PIA, or process a reactantto make a Recycle PIA by obtaining, from any source, a reactant (e.g.any of the compounds of an olefin-containing cracker effluent) from asupplier (e.g. a cracker manufacturer or one among its Family ofEntities), whether or not such reactant has any recycle content, andeither:

-   -   i. from the same supplier of the reactant, also obtain a recycle        content allotment applied to the reactant, or    -   ii. from any person or entity, obtaining a recycle content        allotment without a supply of a reactant from said person or        entity transferring said recycle content allotment.

The allotment in (i) is obtained from a reactant supplier who alsosupplies a reactant to the Recycle PIA manufacturer or within its Familyof Entities. The circumstance described in (i) allows a Recycle PIAmanufacturer to obtain a supply of a reactant that is a non-recyclecontent reactant yet obtain a recycle content allotment from thereactant supplier. In one embodiment or in combination with anymentioned embodiments, the reactant supplier transfers a recycle contentallotment to the Recycle PIA manufacturer and a supply of a reactant(e.g. propylene, ethylene, butylene, etc.) to the Recycle PIAmanufacturer, where the recycle content allotment is not associated withthe reactant supplied, or even not associated with any reactant made bythe reactant supplier. The recycle content allotment does not have to betied to the reactant supplied or tied to an amount of recycle content ina reactant used to make Recycle PIA, olefin-containing effluent Thisallows flexibility among the reactant supplier and Recycle PIAmanufacturer to apportion a recycle content among the variety ofproducts they each make. In each of these cases, however, the recyclecontent allotment is associated with cracking r-pyoil.

In one embodiment or in combination with any mentioned embodiments, thereactant supplier transfers a recycle content allotment to the RecyclePIA manufacturer and a supply of reactant to the Recycle PIAmanufacturer, where the recycle content allotment is associated with thereactant. The transfer of the allotment can occur merely by virtue ofsupplying the reactant having an associated recycle content. Optionally,the reactant being supplied is an r-compound separated from anolefin-containing effluent made by cracking r-pyoil and at least aportion of the recycle content allotment is associated with ther-compound (or r-reactant). The recycle content allotment transferred tothe Recycle PIA manufacturer can be up front with the reactant supplied,optionally in installments, or with each reactant installment, orapportioned as desired among the parties.

The allotment in (ii) is obtained by the Recycle PIA manufacturer (orits Family of Entities) from any person or entity without obtaining asupply of reactant from the person or entity. The person or entity canbe a reactant manufacturer that does not supply reactant to the RecyclePIA manufacturer or its Family of Entities, or the person or entity canbe a manufacturer that does not make the reactant. In either case, thecircumstances of (ii) allows a Recycle PIA manufacturer to obtain arecycle content allotment without having to purchase any reactant fromthe entity or person supplying the recycle content allotment. Forexample, the person or entity may transfer a recycle content allotmentthrough a buy/sell model or contract to the Recycle PIA manufacturer orits Family of Entities without requiring purchase or sale of anallotment (e.g. as a product swap of products that are not a reactant),or the person or entity may outright sell the allotment to the RecyclePIA manufacturer or one among its Family of Entities. Alternatively, theperson or entity may transfer a product, other than a reactant, alongwith its associated recycle content allotment to the Recycle PIAmanufacturer. This can be attractive to a Recycle PIA manufacturer thathas a diversified business making a variety of PIA other than thoserequiring made from the supplied reactant.

The allotment can be deposited into a recycle content inventory (e.g. aninventory of allotments). In one embodiment or in combination with anymentioned embodiments, the allotment is created by the manufacturer ofthe olefin-containing effluent olefin-containing effluent. Themanufacturer can also make a PIA, whether or not a recycle content isapplied to the PIA and whether or not recycle content, if applied to thePIA, is drawn from the recycle content inventory. For example, theolefin-containing effluent manufacturer of the olefin-containingeffluent may:

-   -   a. deposit the allotment into an inventory and merely store it;        or    -   b. olefin-containing effluent deposit the allotment into an        inventory and apply allotments from the inventory to a compound        or compounds within the olefin-containing effluent or to any PIA        made by the manufacturer, or    -   c. sell or transfer the allotment to a third party from the        recycle content inventory into which at least one allotment,        obtained as noted above, was deposited.

If desired, any recycle content allotment can be deducted in any amountand applied to a PIA to make a Recycle PIA or applied to a non-recycleolefin-containing effluent to make an olefin-containing effluent. Forexample, allotments can be generated having a variety of sources forcreating the allotments. Some recycle content allotments (credits) canhave their origin in methanolysis of recycle waste, or from gasificationof other types of recycle waste, or from mechanical recycling of wasteplastic or metal recycling, or from any other chemical or mechanicalrecycling technology. The recycle content inventory may or may not trackthe origin or basis of obtaining a recycle content value, or theinventory may not allow one to associate the origin or basis of anallotment to the allotment applied to r-composition. It is sufficientthat an allotment is deducted from a the recycle content inventory andapplied to a PIA or a non-recycle olefin-containing effluent regardlessof the source or origin of the allotment, provided that a recyclecontent allotment derived from r-pyoil is present in the recycle contentinventory at the time of withdrawal, or a recycle content allotment isobtained by the Recycle PIA manufacturer as specified in step (i) orstep (ii), whether or not that recycle content allotment is actuallydeposited into the recycle content inventory.

In one embodiment or in combination with any mentioned embodiments, therecycle content allotment obtained in step (i) or (ii) is deposited intoan inventory of allotments. In one embodiment or in combination with anymentioned embodiments, the recycle content allotment deducted from therecycle content inventory and applied to PIA or a non-recycleolefin-containing effluent (or any compounds therein) originates fromr-pyoil.

As used throughout, the recycle content inventory can be owned by theowner of a cracker furnace that processes r-pyoil or one among itsFamily of Entities, olefin-containing effluent or by the Recycle PIAmanufacturer, or operated by either of them, or owned or operated byneither but at least in part for the benefit of either of them, orlicensed by or to either of them. Also, cracker olefin-containingeffluent manufacturer or the Recycle PIA manufacturer may also includeeither of their Family of Entities. For example, while either of themmay not own or operate the inventory, one among its Family of Entitiesmay own such a platform, or license it from an independent vendor, oroperate it for either of them. Alternatively, an independent entity mayown and/or operate the inventory and for a service fee operate and/ormanage at least a portion of the inventory for either of them.

In one embodiment or in combination with any mentioned embodiments, theRecycle PIA manufacturer obtains a supply of reactant from a supplier,and also obtains an allotment from the supplier, where such allotment isderived from r-pyoil, and optionally the allotment is associated withthe reactant supplied by the supplier. In one embodiment or incombination with any mentioned embodiments, at least a portion of theallotment obtained by the Recycle PIA manufacturer is either:

-   -   a. applied to PIA made by the supply of the reactant;    -   b. applied to PIA made by the same type of reactant but not made        by the volume of reactant supplied, such as would be the case        where PIA made with the same type of reactant is already made        and stored in inventory or future made PIA; or    -   c. deposited into an inventory from which is deducted an        allotment that is applied to PIA made by other than the type of        reactant supplied, or    -   d. deposited into an inventory and stored.

It is not necessary in all embodiments that r-reactant is used to makeRecycle PIA or that the Recycle PIA was obtained from a recycle contentallotment associated with a reactant. Further, it is not necessary thatan allotment be applied to the feedstock for making the Recycle PIA towhich recycle content is applied. Rather, as noted above, the allotment,even if associated with a reactant when the reactant is obtained, can bedeposited into an electronic inventory. In one embodiment or incombination with any mentioned embodiments, however, reactant associatedwith the allotment is used to make the Recycle PIA. In one embodiment orin combination with any mentioned embodiments, the Recycle PIA isobtained from a recycle content allotment associated with an r-reactant,or r-pyoil, or with cracking r-pyoil. In one embodiment or incombination with any mentioned embodiments,

In one embodiment or in combination with any mentioned embodiments, theolefin-containing effluent manufacturer generates an allotment fromr-pyoil, and either:

-   -   a. applies the allotment to any PIA made directly or indirectly        (e.g. through a reaction scheme of several intermediates) from        cracking r-pyoil olefin-containing effluent; or    -   b. applies the allotment to any PIA not made directly or        indirectly from cracking r-pyoil olefin-containing effluent,        such as would be the case where the PIA is already made and        stored in inventory or future made PIA; or    -   c. deposited into an inventory from which is deducted any        allotment that is applied to PIA; and the deposited allotment        either is or is not associated with the particular allotment        applied to the PIA; or    -   d. is deposited into an inventory and stored for use at a later        time.

There is now also provided a package or a combination of a Recycle PIAand a recycle content identifier associated with Recycle PIA, where theidentifier is or contains a representation that the Recycle PIA containsor is sourced from or associated with a recycle content. The package canbe any suitable package for containing a polymer and/or article, such asa plastic or metal drum, railroad car, isotainer, totes, polytote, bale,IBC totes, bottles, compressed bales, jerricans, and polybags, spools,roving, winding, or cardboard packaging. The identifier can be acertificate document, a product specification stating the recyclecontent, a label, a logo or certification mark from a certificationagency representing that the article or package contains contents or theRecycle PIA contains, or is made from sources or associated with recyclecontent, or it can be electronic statements by the Recycle PIAmanufacturer that accompany a purchase order or the product, or postedon a website as a statement, representation, or a logo representing thatthe Recycle PIA contains or is made from sources that are associatedwith or contain recycle content, or it can be an advertisementtransmitted electronically, by or in a website, by email, or bytelevision, or through a tradeshow, in each case that is associated withRecycle PIA. The identifier need not state or represent that the recyclecontent is derived from r-pyoil. Rather, the identifier can merelyconvey or communicate that the Recycle PIA has or is sourced from arecycle content, regardless of the source. However, the Recycle PIA hasa recycle content allotment that, at least in part, associated withr-pyoil.

In one embodiment or in combination with any mentioned embodiments, onemay communicate recycle content information about the Recycle PIA to athird party where such recycle content information is based on orderived from at least a portion of the allocation or credit. The thirdparty may be a customer of the olefin-containing effluent manufactureror of the Recycle PIA manufacturer or may be any other person or entityor governmental organization other than the entity owning the either ofthem. The communication may electronic, by document, by advertisement,or any other means of communication.

In one embodiment or in combination with any mentioned embodiments,there is provided a system or package comprising:

-   -   a. Recycle PIA, and    -   b. an identifier such as a credit, label or certification        associated with said PIA, where the identifier is a        representation that the PIA has, or is sourced from, a recycle        content (which does not have to identify the source of the        recycle content or allotment) provided that the Recycle PIA made        thereby has an allotment, or is made from a reactant, at least        in part associated with r-pyoil.

The system can be a physical combination, such as a package having atleast some Recycle PIA as its contents and the package has a label, suchas a logo, that identifies the contents as having, or being sourcedfrom, a recycle content. Alternatively, the label or certification canbe issued to a third party or customer as part of a standard operatingprocedure of an entity whenever it transfers or sells Recycle PIA havingor sourced from recycle content. The identifier does not have to bephysically on the Recycle PIA or on a package and does not have to be onany physical document that accompanies or is associated with the RecyclePIA or package. For example, the identifier can be an electronicdocument, certification, or accreditation logo associated with the saleof the Recycle PIA to a customer. The identifier itself need only conveyor communicate that the Recycle PIA has or is sourced from a recyclecontent, regardless of the source. In one embodiment or in combinationwith any mentioned embodiments, articles made from the Recycle PIA mayhave the identifier, such as a stamp or logo embedded or adhered to thearticle or package. In one embodiment or in combination with anymentioned embodiments, the identifier is an electronic recycle contentcredit from any source. In one embodiment or in combination with anymentioned embodiments, the identifier is an electronic recycle contentcredit having its origin in r-pyoil.

The Recycle PIA can be made from a reactant, whether or not the reactantis a recycle content reactant. Once a PIA is made, it can be designatedas having recycle content based on and derived from at least a portionof the allotment. The allotment can be withdrawn or deducted from arecycle content inventory. The amount of the deduction and/or applied tothe PIA can correspond to any of the method e.g. a mass balanceapproach.

In an embodiment, a Recycle PIA can be made by having a recycle contentinventory, and reacting a reactant in a synthetic process to make PIA,withdrawing an allotment from the recycle content inventory having arecycle content value, and applying the recycle content value to the PIAto thereby obtain a Recycle PIA. The amount of allotment deducted frominventory is flexible and will depend on the amount of recycle contentapplied to the PIA. It should be at least sufficient to correspond withat least a portion if not the entire amount of recycle content appliedto the PIA. The recycle content allotment applied to the PIA does nothave to have its origin in r-pyoil, and instead can have its origin inany other method of generating allotments from recycle waste, such asthrough methanolysis or gasification of recycle waste, provided that therecycle content inventory also contains an allotment or has an allotmentdeposit having its origin in r-pyoil. In one embodiment or incombination with any mentioned embodiments, however, the recycle contentallotment applied to the PIA is an allotment obtained from r-pyoil.

The following are examples of applying a recycle content to PIA or tonon-recycle olefin-containing effluents or compounds therein:

-   -   1. A PIA manufacturer applies at least a portion of an allotment        to a PIA to obtain Recycle PIA where the allotment is associated        with r-pyoil and the reactant used to make the PIA did not        contain any recycle content; or    -   2. A PIA manufacturer applies at least a portion of an allotment        to PIA to obtain Recycle PIA, where the allotment is obtained        from a recycle content reactant, whether or not such reactant        volume is used to make the Recycle PIA; or    -   3. A PIA manufacturer applies at least a portion of an allotment        to a PIA to make Recycle PIA where the allotment is obtained        from r-pyoil, and:        -   a. all of the recycle content in the r-pyoil is applied to            determine the amount of recycle content in the Recycle PIA,            or        -   b. only a portion of the recycle content in the r-pyoil            feedstock is applied to determine the amount of recycle            content in the Recycle PIA, the remainder stored in a            recycle content inventory for future use or for application            to other PIA, or to increase the recycle content on an            existing Recycle PIA, or a combination thereof, or        -   c. none of the recycle content in the r-pyoil feedstock is            applied to the PIA and instead is stored in an inventory,            and a recycle content from any source or origin is deducted            from the inventory and applied to PIA to make Recycle PIA;            or    -   4. A Recycle PIA manufacturer applies at least a portion of an        allotment to a reactant used to make a PIA to thereby obtain a        Recycle PIA, where the allotment was obtained with the transfer        or purchase of the same reactant used to make the PIA and the        allotment is associated with the recycle content in a reactant;        or    -   5. A Recycle PIA manufacturer applies at least a portion of an        allotment to a reactant used to make a PIA to thereby obtain a        Recycle PIA, where the allotment was obtained with the transfer        or purchase of the same reactant used to make the PIA and the        allotment is not associated with the recycle content in a        reactant but rather on the recycle content of a monomer used to        make the reactant; or    -   6. A Recycle PIA manufacturer applies at least a portion of an        allotment to a reactant used to make a PIA to thereby obtain a        Recycle PIA, where the allotment was not obtained with the        transfer or purchase of the reactant and the allotment is        associated with the recycle content in the reactant; or    -   7. A Recycle PIA manufacturer applies at least a portion of an        allotment to a reactant used to make a PIA to thereby obtain a        Recycle PIA, where the allotment was not obtained with the        transfer or purchase of the reactant and the allotment is not        associated with the recycle content in the reactant but rather        with the recycle content of any monomers used to make the        reactant; or    -   8. A Recycle PIA manufacturer obtains an allotment having its        origin r-pyoil, and:        -   a. no portion of the allotment is applied to a reactant to            make PIA and instead at least a portion of the allotment is            applied to the PIA to make a Recycle PIA; or        -   b. less than the entire portion is applied to a reactant            used to make PIA and the remainder is stored in inventory or            is applied to future made PIA or is applied to existing            Recycle PIA in inventory to increase its recycle content            value.

In one embodiment or in combination with any mentioned embodiments, theRecycle PIA, or articles made thereby, can be offered for sale or soldas Recycle PIA containing or obtained with recycle content. The sale oroffer for sale can be accompanied with a certification or representationof the recycle content claim made in association with the Recycle PIA.

The designation of at least a portion of the Recycle PIA orolefin-containing effluent as corresponding to at least a portion of theallotment (e.g. allocation or credit) can occur through a variety ofmeans and according to the system employed by the Recycle PIAmanufacturer or the olefin-containing effluent manufacturer, which canvary from manufacturer to manufacturer. For example, the designation canoccur internally merely through a log entry in the books or files of themanufacturer or other inventory software program, or through anadvertisement or statement on a specification, on a package, on theproduct, by way of a logo associated with the product, by way of acertification declaration sheet associated with a product sold, orthrough formulas that compute the amount deducted from inventoryrelative to the amount of recycle content applied to a product.

Optionally, the Recycle PIA can be sold. In one embodiment or incombination with any mentioned embodiments, there is provided a methodof offering to sell or selling polymer and/or articles by:

-   -   a. a Recycle PIA manufacturer or an olefin-containing effluent        manufacturer, or any among their Family of Entities        (collectively the Manufacturer) obtains or generates a recycle        content allotment, and the allotment can be obtained by any of        the means described herein and can be deposited into a recycle        content inventory, the recycle content allotment having its        origin in r-pyoil,    -   b. converting a reactant in a synthetic process to make PIA, and        the reactant can be any reactant or a r-reactant,    -   c. designating (e.g. assigning or associating) a recycle content        to at least a portion of the PIA from a recycle content        inventory to make a Recycle PIA, where the inventory contains at        least one entry that is an allotment associated with r-pyoil.        The designation can be the amount of allotment deducted from        inventory, or the amount of recycle content declared or        determined by the Recycle PIA manufacturer in its accounts.        Thus, the amount of recycle content does not necessarily have to        be applied to the Recycle PIA product in a physical fashion. The        designation can be an internal designation to or by the        Manufacturer or a service provider in contractual relationship        to the Manufacturer, and    -   d. offering to sell or selling the Recycle PIA as containing or        obtained with recycle content corresponding at least in part        with such designation. The amount of recycle content represented        as contained in the Recycle PIA sold or offered for sale has a        relationship or linkage to the designation. The amount of        recycle content can be a 1:1 relationship in the amount of        recycle content declared on a Recycle PIA offered for sale or        sold and the amount of recycle content assigned or designated to        the Recycle PIA by the Recycle PIA manufacturer.

The steps described need not be sequential and can be independent fromeach other. For example, the step a) of obtaining an allotment and thestep of making Recycle PIA can be simultaneous.

As used throughout, the step of deducting an allotment from a recyclecontent inventory does not require its application to a Recycle PIAproduct. The deduction also does not mean that the quantity disappearsor is removed from the inventory logs. A deduction can be an adjustmentof an entry, a withdrawal, an addition of an entry as a debit, or anyother algorithm that adjusts inputs and outputs based on an amountrecycle content associated with a product and one or a cumulative amountof allotments on deposit in the inventory. For example, a deduction canbe a simple step of a reducing/debit entry from one column and anaddition/credit to another column within the same program or books, oran algorithm that automates the deductions and entries/additions and/orapplications or designations to a product slate. The step of applying anallotment to a PIA where such allotment was deducted from inventory alsodoes not require the allotment to be applied physically to a Recycle PIAproduct or to any document issued in association with the Recycle PIAproduct sold. For example, a Recycle PIA manufacturer may ship RecyclePIA product to a customer and satisfy the “application” of the allotmentto the Recycle PIA product by electronically transferring a recyclecontent credit to the customer.

There is also provided a use for r-pyoil, the use including convertingr-pyoil in a gas cracker furnace to make an olefin-containing effluent.There is also provided a use for a r-pyoil that includes converting areactant in a synthetic process to make a PIA and applying at least aportion of an allotment to the PIA, where the allotment is associatedwith r-pyoil or has its origin in an inventory of allotments where atleast one deposit made into the inventory is associated with r-pyoil.

In one embodiment or in combination with any mentioned embodiments,there is provided a Recycle PIA that is obtained by any of the methodsdescribed above.

The reactant can be stored in a storage vessel and transferred to aRecycle PIA manufacturing facility by way of truck, pipe, or ship, or asfurther described below, the olefin-containing effluent productionfacility can be integrated with the PIA facility. The reactant may beshipped or transferred to the operator or facility that makes thepolymer and/or article.

In an embodiment, the process for making Recycle PIA can be anintegrated process. One such example is a process to make Recycle PIAby:

-   -   a. cracking r-pyoil to make an olefin-containing effluent; and    -   b. separating compounds in said olefin-containing effluent to        obtain a separated compound; and    -   c. reacting any reactant in a synthetic process to make a PIA;    -   d. depositing an allotment into an inventory of allotments, said        allotment originating from r-pyoil; and    -   e. applying any allotment from said inventory to the PIA to        thereby obtain a Recycle PIA.

In one embodiment or in combination with any mentioned embodiments, onemay integrate two or more facilities and make Recycle PIA. Thefacilities to make Recycle PIA, or the olefin-containing effluent, canbe stand-alone facilities or facilities integrated to each other. Forexample, one may establish a system of producing and consuming areactant, as follows:

-   -   a. provide an olefin-containing effluent manufacturing facility        configured to produce a reactant;    -   b. provide a PIA manufacturing facility having a reactor        configured to accept a reactant from the olefin-containing        effluent manufacturing facility; and    -   c. a supply system providing fluid communication between these        two facilities and capable of supplying a reactant from the        olefin-containing effluent manufacturing facility to the PIA        manufacturing facility,        wherein the olefin-containing effluent manufacturing facility        generates or participates in a process to generate allotments        and cracks r-pyoil, and:    -   (i) said allotments are applied to the reactants or to the PIA,        or    -   (ii) are deposited into an inventory of allotments, and        optionally an allotment is withdrawn from the inventory and        applied to the reactants or to the PIA.

The Recycle PIA manufacturing facility can make Recycle PIA by acceptingany reactant from the olefin-containing effluent manufacturing facilityand applying a recycle content to Recycle PIA made with the reactant bydeducting allotments from its inventory and applying them to the PIA.

In one embodiment or in combination with any mentioned embodiments,there is also provided a system for producing Recycle PIA as follows:

-   -   a. provide an olefin-containing effluent manufacturing facility        configured to produce an output composition comprising an        olefin-containing effluent;    -   b. provide a reactant manufacturing facility configured to        accept a compound separated from the olefin-containing effluent        and making, through a reaction scheme one or more downstream        products of said compound to make an output composition        comprising a reactant;    -   c. provide a PIA manufacturing facility having a reactor        configured to accept a reactant and making an output composition        comprising PIA; and    -   d. a supply system providing fluid communication between at        least two of these facilities and capable of supplying the        output composition of one manufacturing facility to another one        or more of said manufacturing facilities.

The PIA manufacturing facility can make Recycle PIA. In this system, theolefin-containing effluent manufacturing facility can have its output influid communication with the reactant manufacturing facility which inturn can have its output in fluid communication with the PIAmanufacturing facility. Alternatively, the manufacturing facilities ofa) and b) alone can be in fluid communication, or only b) and c). In thelatter case, the PIA manufacturing facility can make Recycle PIA bydeducting allotments from it recycle content inventory and applying themto the PIA. The allotments obtained and stored in inventory can beobtained by any of the methods described above,

The fluid communication can be gaseous or liquid or both. The fluidcommunication need not be continuous and can be interrupted by storagetanks, valves, or other purification or treatment facilities, so long asthe fluid can be transported from the manufacturing facility to thesubsequent facility through an interconnecting pipe network and withoutthe use of truck, train, ship, or airplane. Further, the facilities mayshare the same site, or in other words, one site may contain two or moreof the facilities. Additionally, the facilities may also share storagetank sites, or storage tanks for ancillary chemicals, or may also shareutilities, steam or other heat sources, etc., yet also be considered asdiscrete facilities since their unit operations are separate. A facilitywill typically be bounded by a battery limit.

In one embodiment or in combination with any mentioned embodiments, theintegrated process includes at least two facilities co-located within 5,or within 3, or within 2, or within 1 mile of each other (measured as astraight line). In one embodiment or in combination with any mentionedembodiments, at least two facilities are owned by the same Family ofEntities.

In an embodiment, there is also provided an integrated Recycle PIAgenerating and consumption system. This system includes:

-   -   a. provide an olefin-containing effluent manufacturing facility        configured to produce an output composition comprising an        olefin-containing effluent;    -   b. provide a reactant manufacturing facility configured to        accept a compound separated from the olefin-containing effluent        and making, through a reaction scheme one or more downstream        products of said compound to make an output composition        comprising a reactant;    -   c. provide a PIA manufacturing facility having a reactor        configured to accept a reactant and making an output composition        comprising PIA; and    -   d. a piping system interconnecting at least two of said        facilities, optionally with intermediate processing equipment or        storage facilities, capable of taking off the output composition        from one facility and accept said output at any one or more of        the other facilities.

The system does not necessarily require a fluid communication betweenthe two facilities, although fluid communication is desirable. Forexample, the compound separated from the olefin-containing effluent canbe delivered to the reactant facility through the interconnecting pipingnetwork that can be interrupted by other processing equipment, such astreatment, purification, pumps, compression, or equipment adapted tocombine streams, or storage facilities, all containing optionalmetering, valving, or interlock equipment. The equipment can be a fixedto the ground or fixed to structures that are fixed to the ground. Theinterconnecting piping does not need to connect to the reactant reactoror the cracker, but rather to a delivery and receiving point at therespective facilities. The interconnecting pipework need not connect allthree facilities to each other, but rather the interconnecting pipeworkcan be between facilities a)-b), or b)-c), or between a)-b)-c).

There is also provided a circular manufacturing process comprising:

-   -   1. providing a r-pyoil, and    -   2. cracking the r-pyoil to produce an olefin-containing        effluent, and        -   (i) reacting a compound separated from said            olefin-containing effluent to make a Recycle PIA, or        -   (ii) associating a recycle content allotment, obtained from            said r-pyoil, to the PIA made from compounds separated from            a non-recycle olefin-containing effluent, to produce a            Recycle PIA; and    -   3. taking back at least a portion of any of said Recycle PIA or        any other articles, compounds, or polymer made from said Recycle        PIA, as a feedstock to make said r-pyoil.

In the above described process, an entirely circular or closed loopprocess is provided in which Recycle PIA can be recycled multiple times.

Examples of articles that are included in PIA are fibers, yarns, tow,continuous filaments, staple fibers, rovings, fabrics, textiles, flake,film (e.g. polyolefin films), sheet, compounded sheet, plasticcontainers, and consumer articles.

In one embodiment or in combination with any mentioned embodiments, theRecycle PIA is a polymer or article of the same family or classificationof polymers or articles used to make r-pyoil.

The terms “recycled waste,” “waste stream,” and “recycled waste stream”are used interchangeably to mean any type of waste or waste-containingstream that is reused in a production process, rather than beingpermanently disposed of (e.g., in a landfill or incinerator). Therecycled waste stream is a flow or accumulation of recycled waste fromindustrial and consumer sources that is at least in part recovered.

A recycled waste stream includes materials, products, and articles(collectively “material(s)” when used alone). Recycled waste materialscan be solid or liquid. Examples of a solid recycled waste streaminclude plastics, rubber (including tires), textiles, wood, biowaste,modified celluloses, wet laid products, and any other material capableof being pyrolyzed. Examples of liquid waste streams include industrialsludge, oils (including those derived from plants and petroleum),recovered lube oil, or vegetable oil or animal oil, and any otherchemical streams from industrial plants.

In one embodiment or in combination with any of the mentionedembodiments, the recycled waste stream that is pyrolyzed includes astream containing at least in part post-industrial, or post-consumer, orboth a post-industrial and post-consumer materials. In one embodiment orin combination with any of the mentioned embodiments, a post-consumermaterial is one that has been used at least once for its intendedapplication for any duration of time regardless of wear, or has beensold to an end use customer, or which is discarded into a recycle bin byany person or entity other than a manufacturer or business engaged inthe manufacture or sale of the material.

In one embodiment or in combination with any of the mentionedembodiments, a post-industrial material is one which has been createdand has not been used for its intended application, or has not been soldto the end use customer, or discarded by a manufacturer or any otherentity engaged in the sale of the material. Examples of post-industrialmaterials include rework, regrind, scrap, trim, out of specificationmaterials, and finished materials transferred from a manufacturer to anydownstream customer (e.g. manufacturer to wholesaler to distributor) butnot yet used or sold to the end use customer.

The form of the recycled waste stream, which can be fed to a pyrolysisunit, is not limited, and can include any of the forms of articles,products, materials, or portions thereof. A portion of an article cantake the form of sheets, extruded shapes, moldings, films, laminates,foam pieces, chips, flakes, particles, fibers, agglomerates, briquettes,powder, shredded pieces, long strips, or randomly shaped pieces having awide variety of shapes, or any other form other than the original formof the article and adapted to feed a pyrolysis unit.

In one embodiment or in combination with any of the mentionedembodiments, the recycled waste material is size reduced. Size reductioncan occur through any means, including chopping, shredding, harrowing,confrication, pulverizing, cutting a feedstock, molding, compression, ordissolution in a solvent.

Recycled waste plastics can be isolated as one type of polymer stream ormay be a stream of mixed recycled waste plastics. The plastics can beany organic synthetic polymer that is solid at 25° C. at 1 atm. Theplastics can be thermosetting, thermoplastic, or elastomeric plastics.Examples of plastics include high density polyethylene and copolymersthereof, low density polyethylene and copolymers thereof, polypropyleneand copolymers thereof, other polyolefins, polystyrene, polyvinylchloride (PVC), polyvinylidene chloride (PVDC), polyesters includingpolyethylene terephthalate, copolyesters and terephthalate copolyesters(e.g. containing residues of TMCD, CHDM, propylene glycol, or NPGmonomers), polyethylene terephthalate, polyamides, poly(methylmethacrylate), polytetrafluoroethylene, acrylobutadienestyrene (ABS),polyurethanes, cellulosics and derivates thereof such as celluloseacetate, cellulose diacetate, cellulose triacetate, cellulosepropionate, cellulose butyrate; regenerated cellulosics such as viscoseand rayons, epoxy, polyamides, phenolic resins, polyacetal,polycarbonates, polyphenylene-based alloys, polypropylene and copolymersthereof, polystyrene, styrenic compounds, vinyl based compounds, styreneacrylonitrile, thermoplastic elastomers, and urea based polymers andmelamine containing polymers.

Suitable recycled waste plastics also include any of those having aresin ID code numbered 1-7 within the chasing arrow triangle establishedby the SPI. In one embodiment or in combination with any of thementioned embodiments, the r-pyoil is made from a recycled waste streamat least a portion of which contains plastics that are not generallyrecycled. These would include plastics having numbers 3 (polyvinylchloride), 5 (polypropylene), 6 (polystyrene), and 7 (other). In oneembodiment or in combination with any of the mentioned embodiments, therecycled waste stream that is pyrolyzed contains less than 10 weightpercent, or not more than 5 weight percent, or not more than 3 weightpercent, or not more than 2 weight percent, or not more than 1 weightpercent, or not more than 0.5 weight percent, or not more than 0.2weight percent, or not more than 0.1 weight percent, or not more and0.05 weight percent plastics with a number 3 designation (polyvinylchloride), or optionally plastics with a number 3 and 6 designation, oroptionally with a number 3, 6 and 7 designation.

Examples of recycled rubber include natural and synthetic rubber. Theform of the rubber is not limited, and includes tires.

Examples of recycled waste wood include soft and hard woods, chipped,pulped, or as finished articles. The source of much recycled waste woodis industrial, construction, or demolition.

Examples of recycled biorecycled waste includes household biorecycledwaste (e.g. food), green or garden biorecycled waste, and biorecycledwaste from the industrial food processing industry.

Examples of recycled textiles includes natural and/or synthetic fibers,rovings, yams, nonwoven webs, cloth, fabrics and products made from orcontaining any of the aforementioned items. Textiles can be woven,knitted, knotted, stitched, tufted, pressing of fibers together such aswould be done in a felting operation, embroidered, laced, crocheted,braided, or nonwoven webs and materials. Textiles include fabrics, andfibers separated from a textile or other product containing fibers,scrap or off spec fibers or yams or fabrics, or any other source ofloose fibers and yarns. A textile also includes staple fibers,continuous fibers, threads, tow bands, twisted and/or spun yarns, greyfabrics made from yarns, finished fabrics produced by wet processinggray fabrics, and garments made from the finished fabrics or any otherfabrics. Textiles include apparels, interior furnishings, and industrialtypes of textiles.

Examples of recycled textiles in the apparel category (things humanswear or made for the body) include sports coats, suits, trousers andcasual or work pants, shirts, socks, sportswear, dresses, intimateapparel, outerwear such as rain jackets, cold temperature jackets andcoats, sweaters, protective clothing, uniforms, and accessories such asscarves, hats, and gloves. Examples of textiles in the interiorfurnishing category include furniture upholstery and slipcovers, carpetsand rugs, curtains, bedding such as sheets, pillow covers, duvets,comforters, mattress covers; linens, table cloths, towels, washcloths,and blankets. Examples of industrial textiles include transportation(auto, airplanes, trains, buses) seats, floor mats, trunk liners, andheadliners; outdoor furniture and cushions, tents, backpacks, luggage,ropes, conveyor belts, calendar roll felts, polishing cloths, rags, soilerosion fabrics and geotextiles, agricultural mats and screens, personalprotective equipment, bullet proof vests, medical bandages, sutures,tapes, and the like.

The recycled nonwoven webs can also be dry laid nonwoven webs. Examplesof suitable articles that may be formed from dry laid nonwoven webs asdescribed herein can include those for personal, consumer, industrial,food service, medical, and other types of end uses. Specific examplescan include, but are not limited to, baby wipes, flushable wipes,disposable diapers, training pants, feminine hygiene products such assanitary napkins and tampons, adult incontinence pads, underwear, orbriefs, and pet training pads. Other examples include a variety ofdifferent dry or wet wipes, including those for consumer (such aspersonal care or household) and industrial (such as food service, healthcare, or specialty) use. Nonwoven webs can also be used as padding forpillows, mattresses, and upholstery, batting for quilts and comforters.In the medical and industrial fields, nonwoven webs of the presentinvention may be used for medical and industrial face masks, protectiveclothing, caps, and shoe covers, disposable sheets, surgical gowns,drapes, bandages, and medical dressings. Additionally, nonwoven webs maybe used for environmental fabrics such as geotextiles and tarps, oil andchemical absorbent pads, as well as building materials such as acousticor thermal insulation, tents, lumber and soil covers and sheeting.Nonwoven webs may also be used for other consumer end use applications,such as for, carpet backing, packaging for consumer, industrial, andagricultural goods, thermal or acoustic insulation, and in various typesof apparel. The dry laid nonwoven webs may also be used for a variety offiltration applications, including transportation (e.g., automotive oraeronautical), commercial, residential, industrial, or other specialtyapplications. Examples can include filter elements for consumer orindustrial air or liquid filters (e.g., gasoline, oil, water), includingnanofiber webs used for microfiltration, as well as end uses like teabags, coffee filters, and dryer sheets. Further, nonwoven webs may beused to form a variety of components for use in automobiles, including,but not limited to, brake pads, trunk liners, carpet tufting, and underpadding.

The recycled textiles can include single type or multiple type ofnatural fibers and/or single type or multiple type of synthetic fibers.Examples of textile fiber combinations include all natural, allsynthetic, two or more type of natural fibers, two or more types ofsynthetic fibers, one type of natural fiber and one type of syntheticfiber, one type of natural fibers and two or more types of syntheticfibers, two or more types of natural fibers and one type of syntheticfibers, and two or more types of natural fibers and two or more types ofsynthetic fibers.

Examples of recycled wet laid products include cardboard, office paper,newsprint and magazine, printing and writing paper, sanitary,tissue/toweling, packaging/container board, specialty papers, apparel,bleached board, corrugated medium, wet laid molded products, unbleachedKraft, decorative laminates, security paper and currency, grand scalegraphics, specialty products, and food and drink products.

Examples of modified cellulose include cellulose acetate, cellulosediacetate, cellulose triacetate, regenerated cellulose such a viscose,rayon, and Lyocel™ products, in any form, such as tow bands, staplefibers, continuous fibers, films, sheets, molded or stamped products,and contained in or on any article such as cigarette filter rods,ophthalmic products, screwdrivers handles, optical films, and coatings.

Examples of recycled vegetable oil or animal oil include the oilsrecovered from animal processing facilities and recycled waste fromrestaurants.

The source for obtaining recycled post-consumer or post-industrialrecycled waste is not limited, and can include recycled waste present inand/or separated from municipal solid recycled waste streams (“MSW”).For example, an MSW stream can be processed and sorted to severaldiscrete components, including textiles, fibers, papers, wood, glass,metals, etc. Other sources of textiles include those obtained bycollection agencies, or by or for or on behalf of textile brand ownersor consortiums or organizations, or from brokers, or from postindustrialsources such as scrap from mills or commercial production facilities,unsold fabrics from wholesalers or dealers, from mechanical and/orchemical sorting or separation facilities, from landfills, or strandedon docks or ships.

In one embodiment or in combination with any of the mentionedembodiments, the feed to the pyrolysis unit can comprise at least 30, orat least 35, or at least 40, or at least 45, or at least 50, or at least55, or at least 60, or at least 65, or at least 70, or at least 75, orat least 80, or at least 85, or at least 90, or at least 95, or at least99, in each case weight percent of at least one, or at least two, or atleast three, or at least four, or at least five, or at least sixdifferent kinds of recycled waste. Reference to a “kind” is determinedby resin ID code 1-7. In one embodiment or in combination with any ofthe mentioned embodiments, the feed to the pyrolysis unit contains lessthan 25, or not more than 20, or not more than 15, or not more than 10,or not more than 5, or not more than 1, in each case weight percent ofpolyvinyl chloride and/or polyethylene terephthalate. In one embodimentor in combination with any of the mentioned embodiments, the recycledwaste stream contains at least one, two, or three kinds of plasticizedplastics.

FIG. 2 depicts an exemplary pyrolysis system 110 that may be employed toat least partially convert one or more recycled waste, particularlyrecycled plastic waste, into various useful pyrolysis-derived products.It should be understood that the pyrolysis system shown in FIG. 2 isjust one example of a system within which the present disclosure can beembodied. The present disclosure may find application in a wide varietyof other systems where it is desirable to efficiently and effectivelypyrolyze recycled waste, particularly recycled plastic waste, intovarious desirable end products. The exemplary pyrolysis systemillustrated in FIG. 2 will now be described in greater detail.

As shown in FIG. 2 , the pyrolysis system 110 may include a wasteplastic source 112 for supplying one or more waste plastics to thesystem 110. The plastic source 112 can be, for example, a hopper,storage bin, railcar, over-the-road trailer, or any other device thatmay hold or store waste plastics. In an embodiment or in combinationwith any of the embodiments mentioned herein, the waste plasticssupplied by the plastic source 112 can be in the form of solidparticles, such as chips, flakes, or a powder. Although not depicted inFIG. 2 , the pyrolysis system 110 may also comprise additional sourcesof other types of recycled wastes that may be utilized to provide otherfeed types to the system 110.

In an embodiment or in combination with any of the embodiments mentionedherein, the waste plastics can include one or more post-consumer wasteplastic such as, for example, high density polyethylene, low densitypolyethylene, polypropylene, other polyolefins, polystyrene, polyvinylchloride (PVC), polyvinylidene chloride (PVDC), polyethyleneterephthalate, polyamides, poly(methyl methacrylate),polytetrafluoroethylene, or combinations thereof. In an embodiment or incombination with any of the embodiments mentioned herein, the wasteplastics may include high density polyethylene, low densitypolyethylene, polypropylene, or combinations thereof. As used herein,“post-consumer” refers to non-virgin plastics that have been previouslyintroduced into the consumer market.

In an embodiment or in combination with any of the embodiments mentionedherein, a waste plastic-containing feed may be supplied from the plasticsource 112. In an embodiment or in combination with any of theembodiments mentioned herein, the waste plastic-containing feed cancomprise, consist essentially of, or consist of high densitypolyethylene, low density polyethylene, polypropylene, otherpolyolefins, polystyrene, polyvinyl chloride (PVC), polyvinylidenechloride (PVDC), polyethylene terephthalate, polyamides, poly(methylmethacrylate), polytetrafluoroethylene, or combinations thereof.

In an embodiment or in combination with any of the embodiments mentionedherein, the waste plastic-containing feed can comprise at least 30, orat least 35, or at least 40, or at least 45, or at least 50, or at least55, or at least 60, or at least 65, or at least 70, or at least 75, orat least 80, or at least 85, or at least 90, or at least 95, or at least99, in each case weight percent of at least one, two, three, or fourdifferent kinds of waste plastic. In an embodiment or in combinationwith any of the embodiments mentioned herein, the plastic waste maycomprise not more than 25, or not more than 20, or not more than 15, ornot more than 10, or not more than 5, or not more than 1, in each caseweight percent of polyvinyl chloride and/or polyethylene terephthalate.In an embodiment or in combination with any of the embodiments mentionedherein, the waste plastic-containing feed can comprise at least one,two, or three kinds of plasticized plastics. Reference to a “kind” isdetermined by resin ID code 1-7.

As depicted in FIG. 2 , the solid waste plastic feed from the plasticsource 112 can be supplied to a feedstock pretreatment unit 114. Whilein the feedstock pretreatment unit 114, the introduced waste plasticsmay undergo a number of pretreatments to facilitate the subsequentpyrolysis reaction. Such pretreatments may include, for example,washing, mechanical agitation, flotation, size reduction or anycombination thereof. In an embodiment or in combination with any of theembodiments mentioned herein, the introduced plastic waste may besubjected to mechanical agitation or subjected to size reductionoperations to reduce the particle size of the plastic waste. Suchmechanical agitation can be supplied by any mixing, shearing, orgrinding device known in the art which may reduce the average particlesize of the introduced plastics by at least 10, or at least 25, or atleast 50, or at least 75, in each case percent.

Next, the pretreated plastic feed can be introduced into a plastic feedsystem 116. The plastic feed system 116 may be configured to introducethe plastic feed into the pyrolysis reactor 118. The plastic feed system116 can comprise any system known in the art that is capable of feedingthe solid plastic feed into the pyrolysis reactor 118. In an embodimentor in combination with any of the embodiments mentioned herein, theplastic feed system 116 can comprise a screw feeder, a hopper, apneumatic conveyance system, a mechanic metal train or chain, orcombinations thereof.

While in the pyrolysis reactor 118, at least a portion of the plasticfeed may be subjected to a pyrolysis reaction that produces a pyrolysiseffluent comprising a pyrolysis oil (e.g., r-pyoil) and a pyrolysis gas(e.g., r-pyrolysis gas). The pyrolysis reactor 118 can be, for example,an extruder, a tubular reactor, a tank, a stirred tank reactor, a riserreactor, a fixed bed reactor, a fluidized bed reactor, a rotary kiln, avacuum reactor, a microwave reactor, an ultrasonic or supersonicreactor, or an autoclave, or a combination of these reactors.

Generally, pyrolysis is a process that involves the chemical and thermaldecomposition of the introduced feed. Although all pyrolysis processesmay be generally characterized by a reaction environment that issubstantially free of oxygen, pyrolysis processes may be furtherdefined, for example, by the pyrolysis reaction temperature within thereactor, the residence time in the pyrolysis reactor, the reactor type,the pressure within the pyrolysis reactor, and the presence or absenceof pyrolysis catalysts.

In an embodiment or in combination with any of the embodiments mentionedherein, the pyrolysis reaction can involve heating and converting theplastic feed in an atmosphere that is substantially free of oxygen or inan atmosphere that contains less oxygen relative to ambient air. In anembodiment or in combination with any of the embodiments mentionedherein, the atmosphere within the pyrolysis reactor 118 may comprise notmore than 5, or not more than 4, or not more than 3, or not more than 2,or not more than 1, or not more than 0.5, in each case weight percent ofoxygen gas.

In an embodiment or in combination with any of the embodiments mentionedherein, the pyrolysis process may be carried out in the presence of aninert gas, such as nitrogen, carbon dioxide, and/or steam. Additionally,or alternatively, in an embodiment or in combination with any of theembodiments mentioned herein, the pyrolysis process can be carried outin the presence of a reducing gas, such as hydrogen and/or carbonmonoxide.

In an embodiment or in combination with any of the embodiments mentionedherein, the temperature in the pyrolysis reactor 118 can be adjusted toas to facilitate the production of certain end products. In anembodiment or in combination with any of the embodiments mentionedherein, the pyrolysis temperature in the pyrolysis reactor 118 can be atleast 325° C., or at least 350° C., or at least 375° C., or at least400° C., or at least 425° C., or at least 450° C., or at least 475° C.,or at least 500° C., or at least 525° C., or at least 550° C., or atleast 575° C., or at least 600° C., or at least 625° C., or at least650° C., or at least 675° C., or at least 700° C., or at least 725° C.,or at least 750° C., or at least 775° C., or at least 800° C.Additionally, or alternatively, in an embodiment or in combination withany of the embodiments mentioned herein, the pyrolysis temperature inthe pyrolysis reactor 118 can be not more than 1,100° C., or not morethan 1,050° C., or not more than 1,000° C., or not more than 950° C., ornot more than 900° C., or not more than 850° C., or not more than 800°C., or not more than 750° C., or not more than 700° C., or not more than650° C., or not more than 600° C., or not more than 550° C., or not morethan 525° C., or not more than 500° C., or not more than 475° C., or notmore than 450° C., or not more than 425° C., or not more than 400° C. Inan embodiment or in combination with any of the embodiments mentionedherein, the pyrolysis temperature in the pyrolysis reactor 118 can rangefrom 325 to 1,100° C., 350 to 900° C., 350 to 700° C., 350 to 550° C.,350 to 475° C., 500 to 1,100° C., 600 to 1,100° C., or 650 to 1,000° C.

In an embodiment or in combination with any of the embodiments mentionedherein, the residence times of the pyrolysis reaction can be at least 1,or at least 2, or at least 3, or at least 4, in each case seconds, or atleast 10, or at least 20, or at least 30, or at least 45, or at least60, or at least 75, or at least 90, in each case minutes. Additionally,or alternatively, in an embodiment or in combination with any of theembodiments mentioned herein, the residence times of the pyrolysisreaction can be not more than 6 hours, or not more than 5, or not morethan 4, or not more than 3, or not more than 2, or not more than 1, ornot more than 0.5, in each case hours. In an embodiment or incombination with any of the embodiments mentioned herein, the residencetimes of the pyrolysis reaction can range from 30 minutes to 4 hours, or30 minutes to 3 hours, or 1 hour to 3 hours, or 1 hour to 2 hours.

In an embodiment or in combination with any of the embodiments mentionedherein, the pressure within the pyrolysis reactor 118 can be maintainedat a pressure of at least 0.1, or at least 0.2, or at least 0.3, in eachcase bar and/or not more than 60, or not more than 50, or not more than40, or not more than 30, or not more than 20, or not more than 10, ornot more than 8, or not more than 5, or not more than 2, or not morethan 1.5, or not more than 1.1, in each case bar. In an embodiment or incombination with any of the embodiments mentioned herein, the pressurewithin the pyrolysis reactor 18 can be maintained at about atmosphericpressure or within the range of 0.1 to 100 bar, or 0.1 to 60 bar, or 0.1to 30 bar, or 0.1 to 10 bar, or 1.5 bar, 0.2 to 1.5 bar, or 0.3 to 1.1bar.

In an embodiment or in combination with any of the embodiments mentionedherein, a pyrolysis catalyst may be introduced into the plastic feedprior to introduction into the pyrolysis reactor 118 and/or introduceddirectly into the pyrolysis reactor 118 to produce an r-catalytic pyoil,or an r-pyoil made by a catalytic pyrolysis process. In an embodiment orin combination with any embodiment mentioned herein or in combinationwith any of the embodiments mentioned herein, the catalyst can comprise:(i) a solid acid, such as a zeolite (e.g., ZSM-5, Mordenite, Beta,Ferrierite, and/or zeolite-Y); (ii) a super acid, such as sulfonated,phosphated, or fluorinated forms of zirconia, titania, alumina,silica-alumina, and/or clays; (iii) a solid base, such as metal oxides,mixed metal oxides, metal hydroxides, and/or metal carbonates,particularly those of alkali metals, alkaline earth metals, transitionmetals, and/or rare earth metals; (iv) hydrotalcite and other clays; (v)a metal hydride, particularly those of alkali metals, alkaline earthmetals, transition metals, and/or rare earth metals; (vi) an aluminaand/or a silica-alumina; (vii) a homogeneous catalyst, such as a Lewisacid, a metal tetrachloroaluminate, or an organic ionic liquid; (viii)activated carbon; or (ix) combinations thereof.

In an embodiment or in combination with any of the embodiments mentionedherein, the pyrolysis reaction in the pyrolysis reactor 118 occurs inthe substantial absence of a catalyst, particularly the above-referencedcatalysts. In such embodiments, a non-catalytic, heat-retaining inertadditive may still be introduced into the pyrolysis reactor 118, such assand, in order to facilitate the heat transfer within the reactor 118.

In an embodiment or in combination with any of the embodiments mentionedherein, the pyrolysis reaction in the pyrolysis reactor 118 may occur inthe substantial absence of a pyrolysis catalyst, at a temperature in therange of 350 to 550° C., at a pressure ranging from 0.1 to 60 bar, andat a residence time of 0.2 seconds to 4 hours, or 0.5 hours to 3 hours.

Referring again to FIG. 2 , the pyrolysis effluent 120 exiting thepyrolysis reactor 118 generally comprises pyrolysis gas, pyrolysisvapors, and residual solids. As used herein, the vapors produced duringthe pyrolysis reaction may interchangeably be referred to as a“pyrolysis oil,” which refers to the vapors when condensed into theirliquid state. In an embodiment or in combination with any of theembodiments mentioned herein, the solids in the pyrolysis effluent 20may comprise particles of char, ash, unconverted plastic solids, otherunconverted solids from the feedstock, and/or spent catalyst (if acatalyst is utilized).

In an embodiment or in combination with any of the embodiments mentionedherein, the pyrolysis effluent 120 may comprise at least 20, or at least25, or at least 30, or at least 40, or at least 45, or at least 50, orat least 55, or at least 60, or at least 65, or at least 70, or at least75, or at least or at least 80, in each case weight percent of thepyrolysis vapors, which may be subsequently condensed into the resultingpyrolysis oil (e.g., r-pyoil). Additionally, or alternatively, in anembodiment or in combination with any of the embodiments mentionedherein, the pyrolysis effluent 120 may comprise not more than 99, or notmore than 95, or not more than 90, or not more than 85, or not more than80, or not more than 75, or not more than 70, or not more than 65, ornot more than 60, or not more than 55, or not more than 50, or not morethan 45, or not more than 40, or not more than 35, or not more than 30,in each case weight percent of the pyrolysis vapors. In an embodiment orin combination with any of the embodiments mentioned herein, thepyrolysis effluent 120 may comprise in the range of 20 to 99 weightpercent, 40 to 90 weight percent, or 55 to 90 weight percent of thepyrolysis vapors.

In an embodiment or in combination with any of the embodiments mentionedherein, the pyrolysis effluent 120 may comprise at least 1, or at least5, or at least 6, or at least 7, or at least 8, or at least 9, or atleast 10, or at least 11, or at least 12, in each case weight percent ofthe pyrolysis gas (e.g., r-pyrolysis gas). As used herein, a “pyrolysisgas” refers to a composition that is produced via pyrolysis and is a gasat standard temperature and pressure (STP). Additionally, oralternatively, in an embodiment or in combination with any of theembodiments mentioned herein, the pyrolysis effluent 20 may comprise notmore than 90, or not more than 85, or not more than 80, or not more than75, or not more than 70, or not more than 65, or not more than 60, ornot more than 55, or not more than 50, or not more than 45, or not morethan 40, or not more than 35, or not more than 30, or not more than 25,or not more than 20, or not more than 15, in each case weight percent ofthe pyrolysis gas. In an embodiment or in combination with any of theembodiments mentioned herein, the pyrolysis effluent 120 may comprise 1to 90 weight percent, or 5 to 60 weight percent, or 10 to 60 weightpercent, or 10 to 30 weight percent, or 5 to 30 weight percent of thepyrolysis gas.

In an embodiment or in combination with any of the embodiments mentionedherein, the pyrolysis effluent 120 may comprise not more than 15, or notmore than 10, or not more than 9, or not more than 8, or not more than7, or not more than 6, or not more than 5, or not more than 4 or notmore than 3, in each case weight percent of the residual solids.

In one embodiment or in combination of any mentioned embodiments, thereis provided a cracker feed stock composition containing pyrolysis oil(r-pyoil), and the r-pyoil composition contains recycle contentcatalytic pyrolysis oil (r-catalytic pyoil) and a recycle contentthermal pyrolysis oil (r-thermal pyoil). An r-thermal pyoil is pyoilmade without the addition of a pyrolysis catalyst. The cracker feedstockcan include at least 5, 10, 15, or 20 weight percent r-catalytic pyoil,optionally that has been hydrotreated. The r-pyoil containing r-thermalpyoil and r-catalytic pyoil can be cracked according to any of theprocesses described herein to provide an olefin-containing effluentstream. The r-catalytic pyoil can be blended with r-thermal pyoil toform a blended stream cracked in the cracker unit. Optionally, theblended stream can contain not more than 10, 5, 3, 2, 1 weight percentof r-catalytic pyoil that has not been hydrotreated.

In one embodiment or in combination with any mentioned embodiment, ther-pyoil does not contain r-catalytic pyoil.

As depicted in FIG. 2 , the conversion effluent 120 from the pyrolysisreactor 118 can be introduced into a solids separator 122. The solidsseparator 122 can be any conventional device capable of separatingsolids from gas and vapors such as, for example, a cyclone separator ora gas filter or combination thereof. In an embodiment or in combinationwith any of the embodiments mentioned herein, the solids separator 122removes a substantial portion of the solids from the conversion effluent120. In an embodiment or in combination with any of the embodimentsmentioned herein, at least a portion of the solid particles 24 recoveredin the solids separator 122 may be introduced into an optionalregenerator 126 for regeneration, generally by combustion. Afterregeneration, at least a portion of the hot regenerated solids 128 canbe introduced directly into the pyrolysis reactor 118. In an embodimentor in combination with any of the embodiments mentioned herein, at leasta portion of the solid particles 124 recovered in the solids separator122 may be directly introduced back into the pyrolysis reactor 118,especially if the solid particles 124 contain a notable amount ofunconverted plastic waste. Solids can be removed from the regenerator126 through line 145 and discharged out of the system.

Turning back to FIG. 2 , the remaining gas and vapor conversion products130 from the solids separator 122 may be introduced into a fractionator132. In the fractionator 132, at least a portion of the pyrolysis oilvapors may be separated from the pyrolysis gas to thereby form apyrolysis gas product stream 134 and a pyrolysis oil vapor stream 136.Suitable systems to be used as the fractionator 132 may include, forexample, a distillation column, a membrane separation unit, a quenchtower, a condenser, or any other known separation unit known in the art.In an embodiment or in combination with any of the embodiments mentionedherein, any residual solids 146 accrued in the fractionator 132 may beintroduced in the optional regenerator 126 for additional processing.

In an embodiment or in combination with any of the embodiments mentionedherein, at least a portion of the pyrolysis oil vapor stream 136 may beintroduced into a quench unit 138 in order to at least partially quenchthe pyrolysis vapors into their liquid form (i.e., the pyrolysis oil).The quench unit 138 may comprise any suitable quench system known in theart, such as a quench tower. The resulting liquid pyrolysis oil stream140 may be removed from the system 110 and utilized in the otherdownstream applications described herein. In an embodiment or incombination with any of the embodiments mentioned herein, the liquidpyrolysis oil stream 140 may not be subjected to any additionaltreatments, such as hydrotreatment and/or hydrogenation, prior to beingutilized in any of the downstream applications described herein.

In an embodiment or in combination with any embodiment mentioned hereinor in combination with any of the embodiments mentioned herein, at leasta portion of the pyrolysis oil vapor stream 136 may be introduced into ahydroprocessing unit 142 for further refinement. The hydroprocessingunit 142 may comprise a hydrocracker, a catalytic cracker operating witha hydrogen feed stream, a hydrotreatment unit, and/or a hydrogenationunit. While in the hydroprocessing unit 142, the pyrolysis oil vaporstream 136 may be treated with hydrogen and/or other reducing gases tofurther saturate the hydrocarbons in the pyrolysis oil and removeundesirable byproducts from the pyrolysis oil. The resultinghydroprocessed pyrolysis oil vapor stream 144 may be removed andintroduced into the quench unit 138. Alternatively, the pyrolysis oilvapor may be cooled, liquified, and then treated with hydrogen and/orother reducing gases to further saturate the hydrocarbons in thepyrolysis oil. In this case, the hydrogenation or hydrotreating isperformed in a liquid phase pyrolysis oil. No quench step is required inthis embodiment post-hydrogenation or post-hydrotreating.

The pyrolysis system 110 described herein may produce a pyrolysis oil(e.g., r-pyoil) and pyrolysis gases (e.g., r-pyrolysis gas) that may bedirectly used in various downstream applications based on theirdesirable formulations. The various characteristics and properties ofthe pyrolysis oils and pyrolysis gases are described below. It should benoted that, while all of the following characteristics and propertiesmay be listed separately, it is envisioned that each of the followingcharacteristics and/or properties of the pyrolysis oils or pyrolysisgases are not mutually exclusive and may be combined and present in anycombination.

The pyrolysis oil may predominantly comprise hydrocarbons having from 4to 30 carbon atoms per molecule (e.g., C4 to C30 hydrocarbons). As usedherein, the term “Cx” or “Cx hydrocarbon,” refers to a hydrocarboncompound including x total carbons per molecule, and encompasses allolefins, paraffins, aromatics, and isomers having that number of carbonatoms. For example, each of normal, iso, and tert butane and butene andbutadiene molecules would fall under the general description “C4.”

In an embodiment or in combination with any of the embodiments mentionedherein, the pyrolysis oil fed to the cracking furnace may have a C4-C30hydrocarbon content of at least 55, or at least 60, or at least 65, orat least 70, or at least 75, or at least 80, or at least 85, or at least90, or at least 95, in each case weight percent based on the weight ofthe pyrolysis oil.

In an embodiment or in combination with any of the embodiments mentionedherein, the pyrolysis oil fed to the furnace can predominantly compriseC₅-C₂₅, C₅-C₂₂, or C₅-C₂₀ hydrocarbons, or may comprise at least about55, or at least 60, or at least 65, or at least 70, or at least 75, orat least 80, or at least 85, or at least 90, or at least 95, in eachcase weight percent of C₅-C₂₅, C₅-C₂₂, or C₅-C₂₀ hydrocarbons, based onthe weight of the pyrolysis oil.

The gas furnace can tolerate a wide variety of hydrocarbon numbers inthe pyrolysis oil feedstock, thereby avoiding the necessity forsubjecting a pyrolysis oil feedstock to separation techniques to delivera smaller or lighter hydrocarbon cut to the cracker furnace. In oneembodiment or in any of the mentioned embodiments, the pyrolysis oilafter delivery from a pyrolysis manufacturer is not subjected aseparation process for separating a heavy hydrocarbon cut from a lighterhydrocarbon cut, relative to each other, prior to feeding the pyrolysisoil to a cracker furnace. The feed of pyrolysis oil to a gas furnaceallows one to employ a pyrolysis oil that contains heavy tail ends orhigher carbon numbers at or above 12. In one embodiment or in any of thementioned embodiments, the pyrolysis oil fed to a cracker furnace is aC₅ to C₂₅ hydrocarbon stream containing at least 3 wt. %, or at least 5wt. %, or at least 8 wt. %, or at least 10 wt. %, or at least 12 wt. %,or at least 15 wt. %, or at least 18 wt. %, or at least 20 wt. %, or atleast 25 wt. % or at least 30 wt. %, or at least 35 wt. %, or at least40 wt. %, or at least 45 wt. %, or at least 50 wt. %, or at least 55 wt.%, or at least 60 wt. % hydrocarbons within a range from C₁₂ to C₂₅,inclusive, or within a range of C₁₄ to C₂₅, inclusive, or within a rangeof C₁₆ to C₂₅, inclusive.

In an embodiment or in combination with any of the embodiments mentionedherein, the pyrolysis oil may have a C₆ to C₁₂ hydrocarbon content of atleast 10, or at least 15, or at least 20, or at least 25, or at least30, or at least 35, or at least 40, or at least 45, or at least 50, orat least 55, in each case weight percent, based on the weight of thepyrolysis oil. Additionally, or alternatively, in an embodiment or incombination with any of the embodiments mentioned herein, the pyrolysisoil may have a C₆-C₁₂ hydrocarbon content of not more than 95, or notmore than 90, or not more than 85, or not more than 80, or not more than75, or not more than 70, or not more than 65, or not more than 60, ineach case weight percent. In an embodiment or in combination with any ofthe embodiments mentioned herein, the pyrolysis oil may have a C₆-C₁₂hydrocarbon content in the range of 10 to 95 weight percent, 20 to 80weight percent, or 35 to 80 weight percent.

In an embodiment or in combination with any of the embodiments mentionedherein, the pyrolysis oil may have a C₁₃ to C₂₃ hydrocarbon content ofat least 1, or at least 5, or at least 10, or at least 15, or at least20, or at least 25, or at least 30, in each case weight percent.Additionally, or alternatively, in an embodiment or in combination withany of the embodiments mentioned herein, the pyrolysis oil may have aC₁₃ to C₂₃ hydrocarbon content of not more than 80, or not more than 75,or not more than 70, or not more than 65, or not more than 60, or notmore than 55, or not more than 50, or not more than 45, or not more than40, in each case weight percent. In an embodiment or in combination withany of the embodiments mentioned herein, the pyrolysis oil may have aC₁₃ to C₂₃ hydrocarbon content in the range of 1 to 80 weight percent, 5to 65 weight percent, or 10 to 60 weight percent.

In an embodiment or in combination with any of the embodiments mentionedherein, the r-pyrolysis oil, or r-pyoil fed to a cracker furnace, orr-pyoil fed to a cracker furnace that, prior to feeding-pyoil, accepts apredominately C2-C4 feedstock (and the mention of r-pyoil or pyrolysisoil throughout includes any of these embodiments), may have a C24+hydrocarbon content of at least 1, or at least 2, or at least 3, or atleast 4, or at least 5, in each case weight percent. Additionally, oralternatively, in an embodiment or in combination with any of theembodiments mentioned herein, the pyrolysis oil may have a C24+hydrocarbon content of not more than 15, or not more than 10, or notmore than 9, or not more than 8, or not more than 7, or not more than 6,in each case weight percent. In an embodiment or in combination with anyof the embodiments mentioned herein, the pyrolysis oil may have a C24+hydrocarbon content in the range of 1 to 15 weight percent, 3 to 15weight percent, 2 to 5 weight percent, or 5 to 10 weight percent.

The pyrolysis oil may also include various amounts of olefins,aromatics, and other compounds. In an embodiment or in combination withany of the embodiments mentioned herein, the pyrolysis oil includes atleast 1, or at least 2, or at least 5, or at least 10, or at least 15,or at least 20, in each case weight percent olefins and/or aromatics.Additionally, or alternatively, in an embodiment or in combination withany of the embodiments mentioned herein, the pyrolysis oil may includenot more than 50, or not more than 45, or not more than 40, or not morethan 35, or not more than 30, or not more than 25, or not more than 20,or not more than 15, or not more than 10, or not more than 5, or notmore than 2, or not more than 1, in each case weight percent olefinsand/or aromatics.

In an embodiment or in combination with any of the embodiments mentionedherein, the pyrolysis oil may have an aromatic content of not more than25, or not more than 20, or not more than 15, or not more than 14, ornot more than 13, or not more than 12, or not more than 11, or not morethan 10, or not more than 9, or not more than 8, or not more than 7, ornot more than 6, or not more than 5, or not more than 4, or not morethan 3, or not more than 2, or not more than 1, in each case weightpercent. In one embodiment or in combination with any mentionedembodiments, the pyrolysis oil has an aromatic content that is nothigher than 15, or not more than 10, or not more than 8, or not morethan 6, in each case weight percent.

In an embodiment or in combination with any of the embodiments mentionedherein, the pyrolysis oil may have a naphthene content of at least 1, orat least 2, or at least 3, or at least 4, or at least 5, or at least 6,or at least 7, or at least 8, or at least 9, or at least 10, or at least11, or at least 12, or at least 13, or at least 14, or at least 15, ineach case weight percent. Additionally, or alternatively, in anembodiment or in combination with any of the embodiments mentionedherein, the pyrolysis oil may have a naphthene content of not more than50, or not more than 45, or not more than 40, or not more than 35, ornot more than 30, or not more than 25, or not more than 20, or not morethan 10, or not more than 5, or not more than 2, or not more than 1, ornot more than 0.5, or no detectable amount, in each case weight percent.In an embodiment or in combination with any of the embodiments mentionedherein, the pyrolysis oil may have a naphthene content of not more than5, or not more than 2, or not more than 1 wt. %, or no detectableamount, or naphthenes. Alternatively, the pyrolysis oil may contain inthe range of 1 to 50 weight percent, 5 to 50 weight percent, or 10 to 45weight percent naphthenes, especially if the r-pyoil was subjected to ahydrotreating process.

In an embodiment or in combination with any of the embodiments mentionedherein, the pyrolysis oil may have a paraffin content of at least 25, orat least 30, or at least 35, or at least 40, or at least 45, or at least50, in each case weight percent. Additionally, or alternatively, in anembodiment or in combination with any of the embodiments mentionedherein, the pyrolysis oil may have a paraffin content of not more than90, or not more than 85, or not more than 80, or not more than 75, ornot more than 70, or not more than 65, or not more than 60, or not morethan 55, in each case weight percent. In an embodiment or in combinationwith any of the embodiments mentioned herein, the pyrolysis oil may havea paraffin content in the range of 25 to 90 weight percent, 35 to 90weight percent, or 40 to 80, or 40-70, or 40-65 weight percent.

In an embodiment or in combination with any of the embodiments mentionedherein, the pyrolysis oil may have an n-paraffin content of at least 5,or at least 10, or at least 15, or at least 25, or at least 30, or atleast 35, or at least 40, or at least 45, or at least 50, in each caseweight percent. Additionally, or alternatively, in an embodiment or incombination with any of the embodiments mentioned herein, the pyrolysisoil may have an n-paraffin content of not more than 90, or not more than85, or not more than 80, or not more than 75, or not more than 70, ornot more than 65, or not more than 60, or not more than 55, in each caseweight percent. In an embodiment or in combination with any of theembodiments mentioned herein, the pyrolysis oil may have an n-paraffincontent in the range of 25 to 90 weight percent, 35 to 90 weightpercent, or 40-70, or 40-65, or 50 to 80 weight percent.

In an embodiment or in combination with any of the embodiments mentionedherein, the pyrolysis oil may have a paraffin to olefin weight ratio ofat least 0.2:1, or at least 0.3:1, or at least 0.4:1, or at least 0.5:1,or at least 0.6:1, or at least 0.7:1, or at least 0.8:1, or at least0.9:1, or at least 1:1. Additionally, or alternatively, in an embodimentor in combination with any of the embodiments mentioned herein, thepyrolysis oil may have a paraffin to olefin weight ratio not more than3:1, or not more than 2.5:1, or not more than 2:1, or not more than1.5:1, or not more than 1.4:1, or not more than 1.3:1. In an embodimentor in combination with any of the embodiments mentioned herein, thepyrolysis oil may have a paraffin to olefin weight ratio in the range of0.2:1 to 5:1, or 1:1 to 4.5:1, or 1.5:1 to 5:1, or 1.5:1:4.5:1, or 0.2:1to 4:1, or 0.2:1 to 3:1, 0.5:1 to 3:1, or 1:1 to 3:1.

In an embodiment or in combination with any of the embodiments mentionedherein, the pyrolysis oil may have an n-paraffin to i-paraffin weightratio of at least 0.001:1, or at least 0.1:1, or at least 0.2:1, or atleast 0.5:1, or at least 1:1, or at least 2:1, or at least 3:1, or atleast 4:1, or at least 5:1, or at least 6:1, or at least 7:1, or atleast 8:1, or at least 9:1, or at least 10:1, or at least 15:1, or atleast 20:1. Additionally, or alternatively, in an embodiment or incombination with any of the embodiments mentioned herein, the pyrolysisoil may have an n-paraffin to i-paraffin weight ratio of not more than100:1, 7 or not more than 5:1, or not more than 50:1, or not more than40:1, or not more than 30:1. In an embodiment or in combination with anyof the embodiments mentioned herein, the pyrolysis oil may have ann-paraffin to i-paraffin weight ratio in the range of 1:1 to 100:1, 4:1to 100:1, or 15:1 to 100:1.

It should be noted that all of the above-referenced hydrocarbon weightpercentages may be determined using gas chromatography-mass spectrometry(GC-MS).

In an embodiment or in combination with any of the embodiments mentionedherein, the pyrolysis oil may exhibit a density at 15° C. of at least0.6 g/cm3, or at least 0.65 g/cm3, or at least 0.7 g/cm3. Additionally,or alternatively, in an embodiment or in combination with any of theembodiments mentioned herein, the pyrolysis oil may exhibit a density at15° C. of not more than 1 g/cm3, or not more than 0.95 g/cm3, or notmore than 0.9 g/cm3, or not more than 0.85 g/cm3. In an embodiment or incombination with any of the embodiments mentioned herein, the pyrolysisoil exhibits a density at 15° C. at a range of 0.6 to 1 g/cm3, 0.65 to0.95 g/cm3, or 0.7 to 0.9 g/cm3.

In an embodiment or in combination with any of the embodiments mentionedherein, the pyrolysis oil may exhibit an API gravity at 15° C. of atleast 28, or at least 29, or at least 30, or at least 31, or at least32, or at least 33. Additionally, or alternatively, in an embodiment orin combination with any of the embodiments mentioned herein, thepyrolysis oil may exhibit an API gravity at 15° C. of not more than 50,or not more than 49, or not more than 48, or not more than 47, or notmore than 46, or not more than 45, or not more than 44. In an embodimentor in combination with any of the embodiments mentioned herein, thepyrolysis oil exhibits an API gravity at 15° C. at a range of 28 to 50,29 to 58, or 30 to 44.

In an embodiment or in combination with any of the embodiments mentionedherein, the pyrolysis oil may have a mid-boiling point of at least 75°C., or at least 80° C., or at least 85° C., or at least 90° C., or atleast 95° C., or at least 100° C., or at least 105° C., or at least 110°C., or at least 115° C. The values can be measured according to theprocedures described in either according to ASTM D-2887, or in theworking examples. A mid-boiling point having the stated value aresatisfied if the value is obtained under either method. Additionally, oralternatively, in an embodiment or in combination with any of theembodiments mentioned herein, the pyrolysis oil may have a mid-boilingpoint of not more than 250° C., or not more than 245° C., or not morethan 240° C., or not more than 235° C., or not more than 230° C., or notmore than 225° C., or not more than 220° C., or not more than 215° C.,or not more than 210° C., or not more than 205° C., or not more than200° C., or not more than 195° C., or not more than 190° C., or not morethan 185° C., or not more than 180° C., or not more than 175° C., or notmore than 170° C., or not more than 165° C., or not more than 160° C., 1or not more than 55° C., or not more than 150° C., or not more than 145°C., or not more than 140° C., or not more than 135° C., or not more than130° C., or not more than 125° C., or not more than 120° C. The valuescan be measured according to the procedures described in eitheraccording to ASTM D-2887, or in the working examples. A mid-boilingpoint having the stated value are satisfied if the value is obtainedunder either method. In an embodiment or in combination with any of theembodiments mentioned herein, the pyrolysis oil may have a mid-boilingpoint in the range of 75 to 250° C., 90 to 225° C., or 115 to 190° C. Asused herein, “mid-boiling point” refers to the median boiling pointtemperature of the pyrolysis oil when 50 weight percent of the pyrolysisoil boils above the mid-boiling point and 50 weight percent boils belowthe mid-boiling point.

In an embodiment or in combination with any of the embodiments mentionedherein, the boiling point range of the pyrolysis oil may be such thatnot more than 10 percent of the pyrolysis oil has a final boiling point(FBP) of 250° C., 280° C., 290° C., 300° C., or 310° C., to determinethe FBP, the procedures described in either according to ASTM D-2887, orin the working examples, can be employed and a FBP having the statedvalues are satisfied if the value is obtained under either method.

Turning to the pyrolysis gas, the pyrolysis gas can have a methanecontent of at least 1, or at least 2, or at least 5, or at least 10, orat least 11, or at least 12, or at least 13, or at least 14, or at least15, or at least 16, or at least 17, or at least 18, or at least 19, orat least 20 weight percent. Additionally, or alternatively, in anembodiment or in combination with any of the embodiments mentionedherein, the pyrolysis gas can have a methane content of not more than50, or not more than 45, or not more than 40, or not more than 35, ornot more than 30, or not more than 25, in each case weight percent. Inan embodiment or in combination with any of the embodiments mentionedherein, the pyrolysis gas can have a methane content in the range of 1to 50 weight percent, 5 to 50 weight percent, or 15 to 45 weightpercent.

In an embodiment or in combination with any of the embodiments mentionedherein, the pyrolysis gas can have a C3 hydrocarbon content of at least1, or at least 2, or at least 3, or at least 4, or at least 5, or atleast 6, or at least 7, or at least 8, or at least 9, or at least 10, orat least 15, or at least 20, or at least 25, in each case weightpercent. Additionally, or alternatively, in an embodiment or incombination with any of the embodiments mentioned herein, the pyrolysisgas can have a C3 hydrocarbon content of not more than 50, or not morethan 45, or not more than 40, or not more than 35, or not more than 30,in each case weight percent. In an embodiment or in combination with anyof the embodiments mentioned herein, the pyrolysis gas can have a C3hydrocarbon content in the range of 1 to 50 weight percent, 5 to 50weight percent, or 20 to 50 weight percent.

In an embodiment or in combination with any of the embodiments mentionedherein, the pyrolysis gas can have a C4 hydrocarbon content of at least1, or at least 2, or at least 3, or at least 4, or at least 5, or atleast 6, or at least 7, or at least 8, or at least 9, or at least 10, orat least 11, or at least 12, or at least 13, or at least 14, or at least15, or at least 16, or at least 17, or at least 18, or at least 19, orat least 20, in each case weight percent. Additionally, oralternatively, in an embodiment or in combination with any of theembodiments mentioned herein, the pyrolysis gas can have a C₄hydrocarbon content of not more than 50, or not more than 45, or notmore than 40, or not more than 35, or not more than 30, or not more than25, in each case weight percent. In an embodiment or in combination withany of the embodiments mentioned herein, the pyrolysis gas can have a C₄hydrocarbon content in the range of 1 to 50 weight percent, 5 to 50weight percent, or 20 to 50 weight percent.

In an embodiment or in combination with any of the embodiments mentionedherein, the pyrolysis oils of the present invention may be a recyclecontent pyrolysis oil composition (r-pyoil).

Various downstream applications that may utilize the above-disclosedpyrolysis oils and/or the pyrolysis gases are described in greaterdetail below. In an embodiment or in combination with any of theembodiments mentioned herein, the pyrolysis oil may be subjected to oneor more treatment steps prior to being introduced into downstream units,such as a cracking furnace. Examples of suitable treatment steps caninclude, but are not limited to, separation of less desirable components(e.g., nitrogen-containing compounds, oxygenates, and/or olefins andaromatics), distillation to provide specific pyrolysis oil compositions,and preheating.

Turning now to FIG. 3 , a schematic depiction of a treatment zone forpyrolysis oil according to an embodiment or in combination with any ofthe embodiments mentioned herein is shown.

As shown in the treatment zone 220 illustrated in FIG. 3 , at least aportion of the r-pyoil 252 made from a recycle waste stream 250 in thepyrolysis system 210 may be passed through a treatment zone 220 such as,for example, a separator, which may separate the r-pyoil into a lightpyrolysis oil fraction 254 and a heavy pyrolysis oil fraction 256. Theseparator 220 employed for such a separation can be of any suitabletype, including a single-stage vapor liquid separator or “flash” column,or a multi-stage distillation column. The vessel may or may not includeinternals and may or may not employ a reflux and/or boil-up stream.

In an embodiment or in combination with any of the embodiments mentionedherein, the heavy fraction may have a C₄ to C₇ content or a C₈₊ contentof at least 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80,or 85 weight percent. The light fraction may include at least about 10,15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, or 85 percent ofC₃ and lighter (C³⁻) or C₇ and lighter (C⁷⁻) content. In someembodiments, separator may concentrate desired components into the heavyfraction, such that the heavy fraction may have a C₄ to C₇ content or aC₈₊ content that is at least 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60,65, 70, 7, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140,145, or 150% greater than the C₄ to C₇ content or the C₈₊ content of thepyrolysis oil withdrawn from the pyrolysis zone. As shown in FIG. 3 , atleast a portion of the heavy fraction may be sent to the crackingfurnace 230 for cracking as or as part of the r-pyoil composition toform an olefin-containing effluent 258, as discussed in further detailbelow.

In an embodiment or in combination with any of the embodiments mentionedherein, the pyrolysis oil is hydrotreated in a treatment zone, while, inother embodiments, the pyrolysis oil is not hydrotreated prior toentering downstream units, such as a cracking furnace. In an embodimentor in combination with any of the embodiments mentioned herein, thepyrolysis oil is not pretreated at all before any downstreamapplications and may be sent directly from the pyrolysis oil source. Thetemperature of the pyrolysis oil exiting the pretreatment zone can be inthe range of 15 to 55° C., 30 to 55° C., 49 to 40° C., 15 to 50° C., 20to 45° C., or 25 to 40° C.

In an embodiment or in combination with any of the embodiments mentionedherein, the r-pyoil may be combined with the non-recycle cracker streamin order to minimize the amount of less desirable compounds present inthe combined cracker feed. For example, when the r-pyoil has aconcentration of less desirable compounds (such as, for example,impurities like oxygen-containing compounds, aromatics, or othersdescribed herein), the r-pyoil may be combined with a cracker feedstockin an amount such that the total concentration of the less desirablecompound in the combined stream is at least 40, 50, 55, 60, 65, 70, 75,80, 85, 90, or 95 percent less than the original content of the compoundin the r-pyoil stream (calculated as the difference between the r-pyoiland combined streams, divided by the r-pyoil content, expressed as apercentage). In some cases, the amount of non-recycle cracker feed tocombine with the r-pyoil stream may be determined by comparing themeasured amount of the one or more less desirable compounds present inthe r-pyoil with a target value for the compound or compounds todetermine a difference and, then, based on that difference, determiningthe amount of non-recycle hydrocarbon to add to the r-pyoil stream. Theamounts of r-pyoil and non-recycle hydrocarbon can be within one or moreranges described herein.

At least a portion of the r-ethylene can be derived directly orindirectly from the cracking of r-pyoil. The process for obtainingr-olefins from cracking (r-pyoil) can be as follows and as described inFIG. 4 .

Turning now to FIG. 4 , a block flow diagram illustrating stepsassociated with the cracking furnace 20 and separation zones 30 of asystem for producing an r-composition obtained from cracking r-pyoil. Asshown in FIG. 4 , a feed stream comprising r-pyoil (the r-pyoilcontaining feed stream) may be introduced into a cracking furnace 20,alone or in combination with a non-recycle cracker feed stream. Apyrolysis unit producing r-pyoil can be co-located with the productionfacility. In other embodiments, the r-pyoil can be sourced from a remotepyrolysis unit and transported to the production facility.

In an embodiment or in combination with any of the embodiments mentionedherein, the r-pyoil containing feed stream may contain r-pyoil in anamount of at least 1, or at least 5, or at least 10, or at least 15, orat least 20, or at least 25, or at least 30, or at least 35, or at least40, or at least 45, or at least 50, or at least 55, or at least 60, orat least 65, or at least 70, or at least 75, or at least 80, or at least85, or at least 90, or at least 95, or at least 97, or at least 98, orat least 99, or at least or 100, in each case weight percent and/or notmore than 95, or not more than 90, or not more than 85, or not more than80, or not more than 75, or not more than 70, or not more than 65, ornot more than 60, or not more than 55, or not more than 50, or not morethan 45, or not more than 40, or not more than 35, or not more than 30,or not more than 25, or not more than 20, in each case weight percent,based on the total weight of the r-pyoil containing feed stream.

In an embodiment or in combination with any of the embodiments mentionedherein, at least 1, or at least 5, or at least 10, or at least 15, or atleast 20, or at least 25, or at least 30, or at least 35, or at least40, or at least 45, or at least 50, or at least 55, or at least 60, orat least 65, or at least 70, or at least 75, or at least 80, or at least85, or at least 90 or at least 97, or at least 98, or at least 99, or100, in each case weight percent and/or not more than 95, or not morethan 90, or not more than 85, or not more than 80, or not more than 75,or not more than 70, or not more than 65, or not more than 60, or notmore than 55, or not more than 50, or not more than 45, or not more than40, or not more than 35, or not more than 30, or not more than 25, ornot more than 20, or not more than 15 or not more than 10, in each caseweight percent of the r-pyoil is obtained from the pyrolysis of a wastestream. In an embodiment or in combination with any of the embodimentsmentioned herein, at least a portion of the r-pyoil is obtained frompyrolysis of a feedstock comprising plastic waste. Desirably, at least90, or at least 95, or at least 97, or at least 98, or at least 99, orat least or 100, in each case wt. %, of the r-pyoil is obtained frompyrolysis of a feedstock comprising plastic waste, or a feedstockcomprising at least 50 wt. % plastic waste, or a feedstock comprising atleast 80 wt. % plastic waste, or a feedstock comprising at least 90 wt.% plastic waste, or a feedstock comprising at least 95 wt. % plasticwaste.

In an embodiment or in combination with any of the embodiments mentionedherein, the r-pyoil can have any one or combination of the compositionalcharacteristics described above with respect to pyrolysis oil.

In an embodiment or in combination with any of the embodiments mentionedherein, the r-pyoil may comprise at least 55, or at least 60, or atleast 65, or at least 70, or at least 75, or at least 80, or at least85, or at least 90, or at least 95, in each case weight percent ofC4-C30 hydrocarbons, and as used herein, hydrocarbons include aliphatic,cycloaliphatic, aromatic, and heterocyclic compounds. In an embodimentor in combination with any of the embodiments mentioned herein, ther-pyoil can predominantly comprise C5-C25, C5-C22, or C5-C20hydrocarbons, or may comprise at least 55, 60, 65, 70, 75, 80, 85, 90,or 95 weight percent of C5-C25, C5-C22, or C5-C20 hydrocarbons.

In an embodiment or in combination with any embodiment mentioned hereinor in combination with any of the mentioned embodiments, the r-pyoilcomposition can comprise C₄-C₁₂ aliphatic compounds (branched orunbranched alkanes and alkenes including diolefins, and alicyclics) andC₁₃-C₂₂ aliphatic compounds in a weight ratio of more than 1:1, or atleast 1.25:1, or at least 1.5:1, or at least 2:1, or at least 2.5:1, orat least 3:1, or at least 4:1, or at least 5:1, or at least 6:1, or atleast 7:1, 10:1, 20:1, or at least 40:1, each by weight and based on theweight of the r-pyoil.

In an embodiment or in combination with any embodiment mentioned hereinor in combination with any of the mentioned embodiments, the r-pyoilcomposition can comprise C13-C22 aliphatic compounds (branched orunbranched alkanes and alkenes including diolefins, and alicyclics) andC4-C12 aliphatic compounds in a weight ratio of more than 1:1, or atleast 1.25:1, or at least 1.5:1, or at least 2:1, or at least 2.5:1, orat least 3:1, or at least 4:1, or at least 5:1, or at least 6:1, or atleast 7:1, 10:1, 20:1, or at least 40:1, each by weight and based on theweight of the r-pyoil.

In an embodiment, the two aliphatic hydrocarbons (branched or unbranchedalkanes and alkenes, and alicyclics) having the highest concentration inthe r-pyoil are in a range of C5-C18, or C5-C16, or C5-C14, or C5-C10,or C5-C8, inclusive.

The r-pyoil can include one or more of paraffins, naphthenes or cyclicaliphatic hydrocarbons, aromatics, aromatic containing compounds,olefins, oxygenated compounds and polymers, heteroatom compounds orpolymers, and other compounds or polymers.

For example, in an embodiment or in combination with any of theembodiments mentioned herein, the r-pyoil may comprise at least 5, or atleast 10, or at least 15, or at least 20, or at least 25, or at least30, or at least 35, or at least 40, or at least 45, or at least 50, orat least 55, or at least 60, or at least 65, or at least 70, or at least75, or at least 80, or at least 85, or at least 90, or at least 95, ineach case weight percent and/or not more than 99, or not more than 97,or not more than 95, or not more than 93, or not more than 90, or notmore than 87, or not more than 85, or not more than 83, or not more than80, or not more than 78, or not more than 75, or not more than 70, ornot more than 65, or not more than 60, or not more than 55, or not morethan 50, or not more than 45, or not more than 40, or not more than 35,or not more than 30, or not more than 25, or not more than 20, or notmore than 15, in each case weight percent of paraffins (or linear orbranched alkanes), based on the total weight of the r-pyoil. In anembodiment or in combination with any of the embodiments mentionedherein, the pyrolysis oil may have a paraffin content in the range of 25to 90, 35 to 90, or 40 to 80, or 40-70, or 40-65 weight percent, or5-50, or 5 to 40, or 5 to 35, or 10 to 35, or 10 to 30, or 5 to 25, or 5to 20, in each case as wt. % based on the weight of the r-pyoilcomposition.

In an embodiment or in combination with any of the embodiments mentionedherein, the r-pyoil can include naphthenes or cyclic aliphatichydrocarbons in amount of zero, or at least 1, or at least 2, or atleast 5, or at least 8, or at least 10, or at least 15, or at least 20,in each case weight percent and/or not more than 50, or not more than45, or not more than 40, or not more than 35, or not more than 30, ornot more than 25, or not more than 20, or not more than 15, or not morethan 10, or not more than 5, or not more than 2, or not more than 1, ornot more than 0.5, or no detectable amount, in each case weight percent.In an embodiment or in combination with any of the embodiments mentionedherein, the r-pyoil may have a naphthene content of not more than 5, ornot more than 2, or not more than 1 wt. %, or no detectable amount, ornaphthenes. Examples of ranges for the amount of naphthenes (or cyclicaliphatic hydrocarbons) contained in the r-pyoil is from 0-35, or 0-30,or 0-25, or 2-20, or 2-15, or 2-10, or 1-10, in each case as wt. % basedon the weight of the r-pyoil composition.

In an embodiment or in combination with any of the embodiments mentionedherein, the r-pyoil may have a paraffin to olefin weight ratio of atleast 0.2:1, or at least 0.3:1, or at least 0.4:1, or at least 0.5:1, orat least 0.6:1, or at least 0.7:1, or at least 0.8:1, or at least 0.9:1,or at least 1:1. Additionally, or alternatively, in an embodiment or incombination with any of the embodiments mentioned herein, the r-pyoilmay have a paraffin to olefin weight ratio not more than 3:1, or notmore than 2.5:1, or not more than 2:1, or not more than 1.5:1, or notmore than 1.4:1, or not more than 1.3:1. In an embodiment or incombination with any of the embodiments mentioned herein, the r-pyoilmay have a paraffin to olefin weight ratio in the range of 0.2:1 to 5:1,or 1:1 to 4.5:1, or 1.5:1 to 5:1, or 1.5:1:4.5:1, or 0.2:1 to 4:1, or0.2:1 to 3:1, 0.5:1 to 3:1, or 1:1 to 3:1.

In an embodiment or in combination with any of the embodiments mentionedherein, the r-pyoil may have an n-paraffin to i-paraffin weight ratio ofat least 0.001:1, or at least 0.1:1, or at least 0.2:1, or at least0.5:1, or at least 1:1, or at least 2:1, or at least 3:1, or at least4:1, or at least 5:1, or at least 6:1, or at least 7:1, or at least 8:1,or at least 9:1, or at least 10:1, or at least 15:1, or at least 20:1.Additionally, or alternatively, in an embodiment or in combination withany of the embodiments mentioned herein, the r-pyoil may have ann-paraffin to i-paraffin weight ratio of not more than 100:1, or notmore than 50:1, or not more than 40:1, or not more than 30:1. In anembodiment or in combination with any of the embodiments mentionedherein, the r-pyoil may have an n-paraffin to i-paraffin weight ratio inthe range of 1:1 to 100:1, 4:1 to 100:1, or 15:1 to 100:1.

In an embodiment, the r-pyoil comprises not more than 30, or not morethan 25, or not more than 20, or not more than 15, or not more than 10,or not more than 8, or not more than 5, or not more than 2, or not morethan 1, in each case weight percent of aromatics, based on the totalweight of the r-pyoil. As used herein, the term “aromatics” refers tothe total amount (in weight) of benzene, toluene, xylene, and styrene.The r-pyoil may include at least 1, or at least 2, or at least 5, or atleast 8, or at least 10, in each case weight percent of aromatics, basedon the total weight of the r-pyoil.

In an embodiment or in combination with any of the embodiments mentionedherein, the r-pyoil can include aromatic containing compounds in anamount of not more than 30, or not more than 25, or not more than 20, ornot more than 15, or not more than 10, or not more than 8, or not morethan 5, or not more than 2, or not more than 1, in each case weight, ornot detectable, based on the total weight of the r-pyoil. Aromaticcontaining compounds includes the above-mentioned aromatics and anycompounds containing an aromatic moiety, such as terephthalate residuesand fused ring aromatics such as the naphthalenes andtetrahydronaphthalene.

In an embodiment or in combination with any of the embodiments mentionedherein, the r-pyoil can include olefins in amount of at least 1, or atleast 2, or at least 5, or at least 8, or at least 10, or at least 15,or at least 20, or at least 30, or at least 40, or at least 45, or atleast 50, or at least 55, or at least 60, or at least or at least 65, ineach case weight percent olefins and/or not more than 85, or not morethan 80, or not more than 75, or not more than 70, or not more than 65,or not more than 60, or not more than 55, or not more than 50, or notmore than 45, or not more than 40, or not more than 35, or not more than30, or not more than 25, or not more than 20, or not more than 15, ornot more than 10, in each case weight percent, based on the weight of ar-pyoil. Olefins include mono- and di-olefins. Examples of suitableranges include olefins present in an amount ranging from 5 to 45, or10-35, or 15 to 30, or 40-85, or 45-85, or 50-85, or 55-85, or 60-85, or65-85, or 40-80, or 45-80, or 50-80, or 55-80, or 60-80, or 65-80,45-80, or 50-80, or 55-80, or 60-80, or 65-80, or 40-75, or 45-75, or50-75, or 55-75, or 60-75, or 65-75, or 40-70, or 45-70, or 50-70, or55-70, or 60-70, or 65-70, or 40-65, or 45-65, or 50-65, or 55-65, ineach case as wt. % based on the weight of the r-pyoil.

In an embodiment or in combination with any of the embodiments mentionedherein, the r-pyoil can include oxygenated compounds or polymers inamount of zero or at least 0.01, or at least 0.1, or at least 1, or atleast 2, or at least 5, in each case weight percent and/or not more than20, or not more than 15, or not more than 10, or not more than 8, or notmore than 6, or not more than 5, or not more than 3, or not more than 2,in each case weight percent oxygenated compounds or polymers, based onthe weight of a r-pyoil. Oxygenated compounds and polymers are thosecontaining an oxygen atom. Examples of suitable ranges includeoxygenated compounds present in an amount ranging from 0-20, or 0-15, or0-10, or 0.01-10, or 1-10, or 2-10, or 0.01-8, or 0.1-6, or 1-6, or0.01-5, in each case as wt. % based on the weight of the r-pyoil.

In an embodiment or in combination with any embodiment mentioned hereinor in combination with any of the mentioned embodiments, the amount ofoxygen atoms in the r-pyoil can be not more than 10, or not more than 8,or not more than 5, or not more than 4, or not more than 3, or not morethan 2.75, or not more than 2.5, or not more than 2.25, or not more than2, or not more than 1.75, or not more than 1.5, or not more than 1.25,or not more than 1, or not more than 0.75, or not more than 0.5, or notmore than 0.25, or not more than 0.1, or not more than 0.05, in eachcase wt. %, based on the weight of the r-pyoil. Examples of the amountof oxygen in the r-pyoil can be from 0-8, or 0-5, or 0-3, or 0-2.5 or0-2, or 0.001-5, or 0.001-4, or 0.001-3, or 0.001-2.75, or 0.001-2.5, or0.001-2, or 0.001-1.5, or 0.001-1, or 0.001-0.5, or 0.001-0.1, in eachcase as wt. % based on the weight of the r-pyoil.

In an embodiment or in combination with any of the embodiments mentionedherein, the r-pyoil can include heteroatom compounds or polymers inamount of at least 1, or at least 2, or at least 5, or at least 8, or atleast 10, or at least 15, or at least 20, in each case weight percentand/or not more than 25, or not more than 20, or not more than 15, ornot more than 10, or not more than 8, or not more than 6, or not morethan 5, or not more than 3, or not more than 2, in each case weightpercent, based on the weight of a r-pyoil. A heterocompound or polymeris defined in this paragraph as any compound or polymer containingnitrogen, sulfur, or phosphorus. Any other atom is not regarded as aheteroatom for purposes of determining the quantity of heteroatoms,heterocompounds, or heteropolymers present in the r-pyoil. The r-pyoilcan contain heteroatoms present in an amount of not more than 5, or notmore than 4, or not more than 3, or not more than 2.75, or not more than2.5, or not more than 2.25, or not more than 2, or not more than 1.75,or not more than 1.5, or not more than 1.25, or not more than 1, or notmore than 0.75, or not more than 0.5, or not more than 0.25, or not morethan 0.1, or not more than 0.075, or not more than 0.05, or not morethan 0.03, or not more than 0.02, or not more than 0.01, or not morethan 0.008, or not more than 0.006, or not more than 0.005, or not morethan 0.003, or not more than 0.002, in each case wt. %, based on theweight of the r-pyoil.

In an embodiment or in combination with any embodiment mentioned hereinor in combination with any of the embodiments mentioned herein, thesolubility of water in the r-pyoil at 1 atm and 25° C. is less than 2wt. %, water, or not more than 1.5, or not more than 1, or not more than0.5, or not more than 0.1, or not more than 0.075, or not more than0.05, or not more than 0.025, or not more than 0.01, or not more than0.005, in each case wt. % water based on the weight of the r-pyoil.Desirably, the solubility of water in the r-pyoil is not more than 0.1wt. % based on the weight of the r-pyoil. In an embodiment or incombination with any embodiment mentioned herein or in combination withany of the embodiments mentioned herein, the r-pyoil contains not morethan 2 wt. %, water, or not more than 1.5, or not more than 1, or notmore than 0.5, desirably or not more than 0.1, or not more than 0.075,or not more than 0.05, or not more than 0.025, or not more than 0.01, ornot more than 0.005, in each case wt. % water based on the weight of ther-pyoil.

In an embodiment or in combination with any embodiment mentioned hereinor in combination with any of the embodiments mentioned herein, thesolids content in the r-pyoil does not exceed 1, or is not more than0.75, or not more than 0.5, or not more than 0.25, or not more than 0.2,or not more than 0.15, or not more than 0.1, or not more than 0.05, ornot more than 0.025, or not more than 0.01, or not more than 0.005, ordoes not exceed 0.001, in each case wt. % solids based on the weight ofthe r-pyoil.

In an embodiment or in combination with any embodiment mentioned hereinor in combination with any of the embodiments mentioned herein thesulfur content of the r-pyoil does not exceed 2.5 wt. %, or is not morethan 2, or not more than 1.75, or not more than 1.5, or not more than1.25, or not more than 1, or not more than 0.75, or not more than 0.5,or not more than 0.25, or not more than 0.1, or not more than 0.05,desirably or not more than 0.03, or not more than 0.02, or not more than0.01, or not more than 0.008, or not more than 0.006, or not more than0.004, or not more than 0.002, or is not more than 0.001, in each casewt. % based on the weight of the r-pyoil.

In an embodiment or in combination with any embodiment mentioned hereinor in combination with any of the embodiments mentioned herein, ther-pyoil can have the following compositional content:

carbon atom content of at least 75 wt. %, or at least or at least 77, orat least 80, or at least 82, or at least 85, in each case wt. %, and/orup to 90, or up to 88, or not more than 86, or not more than 85, or notmore than 83, or not more than 82, or not more than 80, or not more than77, or not more than 75, or not more than 73, or not more than 70, ornot more than 68, or not more than 65, or not more than 63, or up to 60,in each case wt. %, desirably at least 82% and up to 93%, and/or

hydrogen atom content of at least 10 wt. %, or at least 13, or at least14, or at least 15, or at least 16, or at least 17, or at least 18, ornot more than 19, or not more than 18, or not more than 17, or not morethan 16, or not more than 15, or not more than 14, or not more than 13,or up to 11, in each case wt. %,

an oxygen atom content not to exceed 10, or not more than 8, or not morethan 5, or not more than 4, or not more than 3, or not more than 2.75,or not more than 2.5, or not more than 2.25, or not more than 2, or notmore than 1.75, or not more than 1.5, or not more than 1.25, or not morethan 1, or not more than 0.75, or not more than 0.5, or not more than0.25, or not more than 0.1, or not more than 0.05, in each case wt. %,

in each case based on the weight of the r-pyoil.

In an embodiment or in combination with any embodiment mentioned hereinor in combination with any of the mentioned embodiments, the amount ofhydrogen atoms in the r-pyoil can be in a range of from 10-20, or 10-18,or 11-17, or 12-16 or 13-16, or 13-15, or 12-15, in each case as wt. %based on the weight of the r-pyoil.

In an embodiment or in combination with any embodiment mentioned hereinor in combination with any of the embodiments mentioned herein, themetal content of the r-pyoil is desirably low, for example, not morethan 2 wt. %, or not more than 1, or not more than 0.75, or not morethan 0.5, or not more than 0.25, or not more than 0.2, or not more than0.15, or not more than 0.1, or not more than 0.05, in each case wt. %based on the weight of the r-pyoil.

In an embodiment or in combination with any embodiment mentioned hereinor in combination with any of the embodiments mentioned herein, thealkali metal and alkaline earth metal or mineral content of the r-pyoilis desirably low, for example, not more than 2 wt. %, or not more than1, or not more than 0.75, or not more than 0.5, or not more than 0.25,or not more than 0.2, or not more than 0.15, or not more than 0.1, ornot more than 0.05, in each case wt. % based on the weight of ther-pyoil.

In an embodiment or in combination with any embodiment mentioned hereinor in combination with any of the embodiments mentioned herein, theweight ratio of paraffin to naphthene in the r-pyoil can be at least1:1, or at least 1.5:1, or at least 2:1, or at least 2.2:1, or at least2.5:1, or at least 2.7:1, or at least 3:1, or at least 3.3:1, or atleast 3.5:1, or at least 3.75:1, or at least 4:1, or at least 4.25:1, orat least 4.5:1, or at least 4.75:1, or at least 5:1, or at least 6:1, orat least 7:1, or at least 8:1, or at least 9:1, or at least 10:1, or atleast 13:1, or at least 15:1, or at least 17:1, based on the weight ofthe r-pyoil.

In an embodiment or in combination with any embodiment mentioned hereinor in combination with any of the embodiments mentioned herein, theweight ratio of paraffin and naphthene combined to aromatics can be atleast 1:1, or at least 1.5:1, or at least 2:1, or at least 2.5:1, or atleast 2.7:1, or at least 3:1, or at least 3.3:1, or at least 3.5:1, orat least 3.75:1, or at least 4:1, or at least 4.5:1, or at least 5:1, orat least 7:1, or at least 10:1, or at least 15:1, or at least 20:1, orat least 25:1, or at least 30:1, or at least 35:1, or at least 40:1,based on the weight of the r-pyoil. In an embodiment or in combinationwith any embodiment mentioned herein or in combination with any of thementioned embodiments, the ratio of paraffin and naphthene combined toaromatics in the r-pyoil can be in a range of from 50:1-1:1, or40:1-1:1, or 30:1-1:1, or 20:1-1:1, or 30:1-3:1, or 20:1-1:1, or20:1-5:1, or 50:1-5:1, or 30:1-5:1, or 1:1-7:1, or 1:1-5:1, 1:1-4:1, or1:1-3:1.

In an embodiment or in combination with any of the embodiments mentionedherein, the r-pyoil may have a boiling point curve defined by one ormore of its 10%, its 50%, and its 90% boiling points, as defined below.As used herein, “boiling point” refers to the boiling point of acomposition as determined by ASTM D2887 or according to the proceduredescribed in the working examples. A boiling point having the statedvalues are satisfied if the value is obtained under either method.Additionally, as used herein, an “x % boiling point,” refers to aboiling point at which x percent by weight of the composition boils pereither of these methods.

As used throughout, an x % boiling at a stated temperature means atleast x % of the composition boils at the stated temperature. In anembodiment or in combination with any of the embodiments mentionedherein, the 90% boiling point of the cracker feed stream or compositioncan be not more than 350, or not more than 325, or not more than 300, ornot more than 295, or not more than 290, or not more than 285, or notmore than 280, or not more than 275, or not more than 270, or not morethan 265, or not more than 260, or not more than 255, or not more than250, or not more than 245, or not more than 240, or not more than 235,or not more than 230, or not more than 225, or not more than 220, or notmore than 215, not more than 200, not more than 190, not more than 180,not more than 170, not more than 160, not more than 150, or not morethan 140, in each case ° C. and/or at least 200, or at least 205, or atleast 210, or at least 215, or at least 220, or at least 225, or atleast 230, in each case ° C. and/or not more than 25, 20, 15, 10, 5, or2 weight percent of the r-pyoil may have a boiling point of 300° C. orhigher.

Referring again to FIG. 3 , the r-pyoil may be introduced into acracking furnace or coil or tube alone (e.g., in a stream comprising atleast 85, or at least 90, or at least 95, or at least 99, or 100, ineach case wt. % percent pyrolysis oil based on the weight of the crackerfeed stream), or combined with one or more non-recycle cracker feedstreams. When introduced into a cracker furnace, coil, or tube with anon-recycle cracker feed stream, the r-pyoil may be present in an amountof at least 1, or at least 2, or at least 5, or at least 8, or at least10, or at least 12, or at least 15, or at least 20, or at least 25, orat least 30, in each case wt. % and/or not more than 40, or not morethan 35, or not more than 30, or not more than 25, or not more than 20,or not more than 15, or not more than 10, or not more than 8, or notmore than 5, or not more than 2, in each case weight percent based onthe total weight of the combined stream. Thus, the non-recycle crackerfeed stream or composition may be present in the combined stream in anamount of at least 20, or at least 25, or at least 30, or at least 35,or at least 40, or at least 45, or at least 50, or at least 55, or atleast 60, or at least 65, or at least 70, or at least 75, or at least80, or at least 85, or at least 90, in each case weight percent and/ornot more than 99, or not more than 95, or not more than 90, or not morethan 85, or not more than 80, or not more than 75, or not more than 70,or not more than 65, or not more than 60, or not more than 55, or notmore than 50, or not more than 45, or not more than 40, in each caseweight percent based on the total weight of the combined stream. Unlessotherwise noted herein, the properties of the cracker feed stream asdescribed below apply either to the non-recycle cracker feed streamprior to (or absent) combination with the stream comprising r-pyoil, aswell as to a combined cracker stream including both a non-recyclecracker feed and a r-pyoil feed.

In an embodiment or in combination with any of the embodiments mentionedherein, the cracker feed stream may comprise a predominantly C₂-C₄hydrocarbon containing composition, or a predominantly C₅-C₂₂hydrocarbon containing composition. As used herein, the term“predominantly C₂-C₄ hydrocarbon,” refers to a stream or compositioncontaining at least 50 weight percent of C₂-C₄ hydrocarbon components.Examples of specific types of C₂-C₄ hydrocarbon streams or compositionsinclude propane, ethane, butane, and LPG. In an embodiment or incombination with any of the embodiments mentioned herein, the crackerfeed may comprise at least 50, or at least 55, or at least 60, or atleast 65, or at least 70, or at least 75, or at least 80, or at least85, or at least 90, or at least 95, in each case wt. % based on thetotal weight of the feed, and/or not more than 100, or not more than 99,or not more than 95, or not more than 92, or not more than 90, or notmore than 85, or not more than 80, or not more than 75, or not more than70, or not more than 65, or not more than 60, in each case weightpercent C₂-C₄ hydrocarbons or linear alkanes, based on the total weightof the feed. The cracker feed can comprise predominantly propane,predominantly ethane, predominantly butane, or a combination of two ormore of these components. These components may be non-recyclecomponents. The cracker feed can comprise predominantly propane, or atleast 50 mole % propane, or at least 80 mole % propane, or at least 90mole % propane, or at least 93 mole % propane, or at least 95 mole %propane (inclusive of any recycle streams combined with virgin feed).The cracker feed can comprise HD5 quality propane as a virgin or freshfeed. The cracker can comprise at more than 50 mole % ethane, or atleast 80 mole % ethane, or at least 90 mole % ethane, or at least 95mole % ethane. These components may be non-recycle components.

In an embodiment or in combination with any of the embodiments mentionedherein, the cracker feed stream may comprise a predominantly C₅-C₂₂hydrocarbon containing composition. As used herein, “predominantlyC₅-C₂₂ hydrocarbon” refers to a stream or composition comprising atleast 50 weight percent of C₅-C₂₂ hydrocarbon components. Examplesinclude gasoline, naphtha, middle distillates, diesel, kerosene. In anembodiment or in combination with any of the embodiments mentionedherein, the cracker feed stream or composition may comprise at least 20,or at least 25, or at least 30, or at least 35, or at least 40, or atleast 45, or at least 50, or at least 55, or at least 60, or at least65, or at least 70, or at least 75, or at least 80, or at least 85, orat least 90, or at least 95, in each case wt. % and/or not more than100, or not more than 99, or not more than 95, or not more than 92, ornot more than 90, or not more than 85, or not more than 80, or not morethan 75, or not more than 70, or not more than 65, or not more than 60,in each case weight percent C₅-C₂₂, or C₅-C₂₀ hydrocarbons, based on thetotal weight of the stream or composition. In an embodiment or incombination with any of the embodiments mentioned herein, the crackerfeed may have a C15 and heavier (C15+) content of at least 0.5, or atleast 1, or at least 2, or at least 5, in each case weight percentand/or not more than 40, or not more than 35, or not more than 30, ornot more than 25, or not more than 20, or not more than 18, or not morethan 15, or not more than 12, or not more than 10, or not more than 5,or not more than 3, in each case weight percent, based on the totalweight of the feed.

The cracker feed may have a boiling point curve defined by one or moreof its 10%, its 50%, and its 90% boiling points, the boiling point beingobtained by the methods described above Additionally, as used herein, an“x % boiling point,” refers to a boiling point at which x percent byweight of the composition boils per the methods described above. In anembodiment or in combination with any of the embodiments mentionedherein, the 90% boiling point of the cracker feed stream or compositioncan be not more than 360, or not more than 355, or not more than 350, ornot more than 345, or not more than 340, or not more than 335, or notmore than 330, or not more than 325, or not more than 320, or not morethan 315, or not more than 300, or not more than 295, or not more than290, or not more than 285, or not more than 280, or not more than 275,or not more than 270, or not more than 265, or not more than 260, or notmore than 255, or not more than 250, or not more than 245, or not morethan 240, or not more than 235, or not more than 230, or not more than225, or not more than 220, or not more than 215, in each case ° C.and/or at least 200, or at least 205, or at least 210, or at least 215,or at least 220, or at least 225, or at least 230, in each case ° C.

In an embodiment or in combination with any of the embodiments mentionedherein, the 10% boiling point of the cracker feed stream or compositioncan be at least 40, at least 50, at least 60, at least 70, at least 80,at least 90, at least 100, at least 110, at least 120, at least 130, atleast 140, at least 150, or at least 155, in each case ° C. and/or notmore than 250, not more than 240, not more than 230, not more than 220,not more than 210, not more than 200, not more than 190, not more than180, or not more than 170 in each case ° C.

In an embodiment or in combination with any of the embodiments mentionedherein, the 50% boiling point of the cracker feed stream or compositioncan be at least 60, at least 65, at least 70, at least 75, at least 80,at least 85, at least 90, at least 95, at least 100, at least 110, atleast 120, at least 130, at least 140, at least 150, at least 160, atleast 170, at least 180, at least 190, at least 200, at least 210, atleast 220, or at least 230, in each case ° C., and/or not more than 300,not more than 290, not more than 280, not more than 270, not more than260, not more than 250, not more than 240, not more than 230, not morethan 220, not more than 210, not more than 200, not more than 190, notmore than 180, not more than 170, not more than 160, not more than 150,or not more than 145° C. The 50% boiling point of the cracker feedstream or composition can be in the range of 65 to 160, 70 to 150, 80 to145, 85 to 140, 85 to 230, 90 to 220, 95 to 200, 100 to 190, 110 to 180,200 to 300, 210 to 290, 220 to 280, 230 to 270, in each case in ° C.

In an embodiment or in combination with any of the embodiments mentionedherein, the 90% boiling point of the cracker feedstock or stream orcomposition can be at least 350° C., the 10% boiling point can be atleast 60° C.; and the 50% boiling point can be in the range of from 95°C. to 200° C. In an embodiment or in combination with any of theembodiments mentioned herein, the 90% boiling point of the crackerfeedstock or stream or composition can be at least 150° C., the 10%boiling point can be at least 60° C., and the 50% boiling point can bein the range of from 80 to 145° C. In an embodiment or in combinationwith any of the embodiments mentioned herein, the cracker feedstock orstream has a 90% boiling point of at least 350° C., a 10% boiling pointof at least 150° C., and a 50% boiling point in the range of from 220 to280° C.

In an embodiment or in combination with any embodiment mentioned hereinor in combination with any of the embodiments mentioned herein, ther-pyoil is cracked in a gas furnace. A gas furnace is a furnace havingat least one coil which receives (or operated to receive), at the inletof the coil at the entrance to the convection zone, a predominatelyvapor-phase feed (more than 50% of the weight of the feed is vapor)(“gas coil”). In an embodiment or in combination with any embodimentmentioned herein or in combination with any of the mentionedembodiments, the gas coil can receive a predominately C₂-C₄ feedstock,or a predominately a C₂-C₃ feedstock to the inlet of the coil in theconvection section, or alternatively, having at least one coil receivingmore than 50 wt. % ethane and/or more than 50% propane and/or more than50% LPG, or in any one of these cases at least 60 wt. %, or at least 70wt. %, or at least 80 wt. %, based on the weight of the cracker feed tothe coil, or alternatively based on the weight of the cracker feed tothe convection zone. The gas furnace may have more than one gas coil. Inan embodiment or in combination with any embodiment mentioned herein orin combination with any of the mentioned embodiments, at least 25% ofthe coils, or at least 50% of the coils, or at least 60% of the coils,or all the coils in the convection zone or within a convection box ofthe furnace are gas coils. In an embodiment or in combination with anyembodiment mentioned herein or in combination with any of the mentionedembodiments, the gas coil receives, at the inlet of the coil at theentrance to the convection zone, a vapor-phase feed in which at least 60wt. %, or at least 70 wt. %, or at least 80 wt. %, or at least 90 wt. %,or at least 95 wt. %, or at least 97 wt. %, or at least 98 wt. %, or atleast 99 wt. %, or at least 99.5 wt. %, or at least 99.9 wt. % of feedis vapor.

In an embodiment or in combination with any embodiment mentioned hereinor in combination with any of the mentioned embodiments, the r-pyoil iscracked in a split furnace. A split furnace is a type of gas furnace. Asplit furnace contains at least one gas coil and at least one liquidcoil within the same furnace, or within the same convection zone, orwithin the same convection box. A liquid coil is a coil which receives,at the inlet of coil at the entrance to the convection zone, apredominately liquid phase feed (more than 50% of the weight of the feedis liquid) (“liquid coil”). In an embodiment or in combination with anyembodiment mentioned herein or in combination with any of the mentionedembodiments, the liquid coil can receive a predominately C₅₊ feedstockto the inlet of the coil at the entrance of the convection section(“liquid coil”). In an embodiment or in combination with any embodimentmentioned herein or in combination with any of the mentionedembodiments, the liquid coil can receive a predominately C₆-C₂₂feedstock, or a predominately a C₇-C₁₆ feedstock to the inlet of thecoil in the convection section, or alternatively, having at least onecoil receiving more than 50 wt. % naphtha, and/or more than 50% naturalgasoline, and/or more than 50% diesel, and/or more than JP-4, and/ormore than 50% Stoddard Solvent, and/or more than 50% kerosene, and/ormore than 50% fresh creosote, and/or more than 50% JP-8 or Jet-A, and/ormore than 50% heating oil, and/or more than 50% heavy fuel oil, and/ormore than 50% bunker C, and/or more than 50% lubricating oil, or in anyone of these cases at least 60 wt. %, or at least 70 wt. %, or at least80 wt. %, or at least 90 wt. %, or at least 95 wt. %, or at least 98 wt.%, or at least 99 wt. %, based on the weight of the cracker feed to theliquid coil, or alternatively based on the weight of the cracker feed tothe convection zone. In an embodiment or in combination with anyembodiment mentioned herein or in combination with any of the mentionedembodiments, at least one coil and not more than 75% of the coils, ornot more than 50% of the coils, or not more than at least 40% of thecoils in the convection zone or within a convection box of the furnaceare liquid coils. In an embodiment or in combination with any embodimentmentioned herein or in combination with any of the mentionedembodiments, the liquid coil receives, at the inlet of the coil at theentrance to the convection zone, a liquid-phase feed in which at least60 wt. %, or at least 70 wt. %, or at least 80 wt. %, or at least 90 wt.%, or at least 95 wt. %, or at least 97 wt. %, or at least 98 wt. %, orat least 99 wt. %, or at least 99.5 wt. %, or at least 99.9 wt. % offeed is liquid.

In an embodiment or in combination with any embodiment mentioned hereinor in combination with any of the mentioned embodiments, the r-pyoil iscracked in a thermal gas cracker.

In an embodiment or in combination with any embodiment mentioned hereinor in combination with any of the mentioned embodiments, the r-pyoil iscracked in a thermal steam gas cracker in the presence of steam. Steamcracking refers to the high-temperature cracking (decomposition) ofhydrocarbons in the presence of steam.

In an embodiment or in combination with any embodiment mentioned hereinor in combination with any of the mentioned embodiments, ther-composition is derived directly or indirectly from cracking r-pyoil ina gas furnace. The coils in the gas furnace can consist entirely of gascoils or the gas furnace can be a split furnace.

When the r-pyoil containing feed stream is combined with the non-recyclecracker feed, such a combination may occur upstream of, or within, thecracking furnace or within a single coil or tube. Alternatively, ther-pyoil containing feed stream and non-recycle cracker feed may beintroduced separately into the furnace, and may pass through a portion,or all, of the furnace simultaneously while being isolated from oneanother by feeding into separate tubes within the same furnace (e.g., asplit furnace). Ways of introducing the r-pyoil containing feed streamand the non-recycle cracker feed into the cracking furnace according toan embodiment or in combination with any of the embodiments mentionedherein are described in further detail below.

Turning now to FIG. 5 , a schematic diagram of a cracker furnacesuitable for use in an embodiment or in combination with any of theembodiments mentioned herein is shown.

In one embodiment or in combination of any of the mentioned embodiments,there is provided a method for making one or more olefins including:

-   -   (a) feeding a first cracker feed comprising a recycle content        pyrolysis oil composition (r-pyoil) to a cracker furnace;    -   (b) feeding a second cracker feed into said cracker furnace,        wherein said second cracker feed comprises none of said r-pyoil        or less of said r-pyoil, by weight, than said first cracker feed        stream; and    -   (c) cracking said first and said second cracker feeds in        respective first and second tubes to form an olefin-containing        effluent stream.

The r-pyoil can be combined with a cracker stream to make a combinedcracker stream, or as noted above, a first cracker stream. The firstcracker stream can be 100% r-pyoil or a combination of a non-recyclecracker stream and r-pyoil. The feeding of step (a) and/or step (b) canbe performed upstream of the convection zone or within the convectionzone. The r-pyoil can be combined with a non-recycle cracker stream toform a combined or first cracker stream and fed to the inlet of aconvection zone, or alternatively the r-pyoil can be separately fed tothe inlet of a coil or distributor along with a non-recycle crackerstream to form a first cracker stream at the inlet of the convectionzone, or the r-pyoil can be fed downstream of the inlet of theconvection zone into a tube containing non-recycle cracker feed, butbefore a crossover, to make a first cracker stream or combined crackerstream in a tube or coil. Any of these methods includes feeding thefirst cracker stream to the furnace.

The amount of r-pyoil added to the non-recycle cracker stream to makethe first cracker stream or combined cracker stream can be as describedabove; e.g. in an amount of at least 1, 5, 10, 15, 20, 25, 30, 35, 40,45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95, in each case weightpercent and/or not more than 95, 90, 85, 80, 75, 70, 65, 60, 55, 60, 55,50, 45, 40, 35, 30, 25, 20, 15, or 1, in each case weight percent, basedon the total weight of the first cracker feed or combined cracker feed(either as introduced into the tube or within the tube as noted above).Further examples include 5-50, 5-40, 5-35, 5-30, 5-25, 5-20, or 5-15 wt.%.

The first cracker stream is cracked in a first coil or tube. The secondcracker stream is cracked in a second coil or tube. Both the first andsecond cracker streams and the first and second coils or tubes can bewithin the same cracker furnace.

The second cracker stream can have none of the r-pyoil or less of saidr-pyoil, by weight, than the first cracker feed stream. Also, the secondcracker stream can contain only non-recycle cracker feed in the secondcoil or tube. The second cracker feed stream can be predominantly C₂ toC₄, or hydrocarbons (e.g. non-recycle content), or ethane, propane, orbutane, in each case in amounts of at least 55, 60, 65, 70, 75, 80, 85,or at least 90 weight percent based on the second cracker feed within asecond coil or tube. If r-pyoil is included in the second cracker feed,the amount of such r-pyoil can be at least 10% less, 20, 30, 40, 50, 60,70, 80, 90, 95, 97, or 99% less by weight than the amount of r-pyoil inthe first cracker feed.

In an embodiment or in combination with any embodiment mentioned hereinor in combination with any of the mentioned embodiments, although notshown, a vaporizer can be provided to vaporize a condensed feedstock ofC2-C5 hydrocarbons 350 to ensure that the feed to the inlet of the coilsin the convection box 312, or the inlet of the convection zone 310, is apredominately vapor phase feed.

The cracking furnace shown in FIG. 5 includes a convection section orzone 310, a radiant section or zone 320, and a cross-over section orzone 330 located between the convection and radiant sections 310 and320. The convection section 310 is the portion of the furnace 300 thatreceives heat from hot flue gases and includes a bank of tubes or coils324 through which a cracker stream 350 passes. In the convection section310, the cracker stream 350 is heated by convection from the hot fluegasses passing therethrough. The radiant section 320 is the section ofthe furnace 300 into which heat is transferred into the heater tubesprimarily by radiation from the high-temperature gas. The radiantsection 320 also includes a plurality of burners 326 for introducingheat into the lower portion of the furnace. The furnace includes a firebox 322 which surrounds and houses the tubes within the radiant section320 and into which the burners are oriented. The cross-over section 330includes piping for connecting the convection 310 and radiant sections320 and may transfer the heated cracker stream internally or externallyfrom one section to the other within the furnace 300.

As hot combustion gases ascend upwardly through the furnace stack, thegases may pass through the convection section 310, wherein at least aportion of the waste heat may be recovered and used to heat the crackerstream passing through the convection section 310. In an embodiment orin combination with any of the embodiments mentioned herein, thecracking furnace 300 may have a single convection (preheat) section 310and a single radiant 320 section, while, in other embodiments, thefurnace may include two or more radiant sections sharing a commonconvection section. At least one induced draft (I.D.) fan 316 near thestack may control the flow of hot flue gas and heating profile throughthe furnace, and one or more heat exchangers 340 may be used to cool thefurnace effluent 370. In an embodiment or in combination with any of theembodiments mentioned herein (not shown), a liquid quench may be used inaddition to, or alternatively with, the exchanger (e.g., transfer lineheat exchanger or TLE) shown in FIG. 5 , for cooling the crackedolefin-containing effluent.

The furnace 300 also includes at least one furnace coil 324 throughwhich the cracker streams pass through the furnace. The furnace coils324 may be formed of any material inert to the cracker stream andsuitable for withstanding high temperatures and thermal stresses withinthe furnace. The coils may have any suitable shape and can, for example,have a circular or oval cross-sectional shape.

The coils in the convection section 310, or tubes within the coil, mayhave a diameter of at least 1, or at least 1.5, or at least 2, or atleast 2.5, or at least 3, or at least 3.5, or at least 4, or at least4.5, or at least 5, or at least 5.5, or at least 6, or at least 6.5, orat least 7, or at least 7.5, or at least 8, or at least 8.5, or at least9, or at least 9.5, or at least 10, or at least 10.5, in each case cmand/or not more than 12, or not more than 11.5, or not more than 11, 1or not more than 0.5, or not more than 10, or not more than 9.5, or notmore than 9, or not more than 8.5, or not more than 8, or not more than7.5, or not more than 7, or not more than 6.5, in each case cm. All or aportion of one or more coils can be substantially straight, or one ormore of the coils may include a helical, twisted, or spiral segment. Oneor more of the coils may also have a U-tube or split U-tube design. Inan embodiment or in combination with any of the embodiments mentionedherein, the interior of the tubes may be smooth or substantially smooth,or a portion (or all) may be roughened in order to minimize coking.Alternatively, or in addition, the inner portion of the tube may includeinserts or fins and/or surface metal additives to prevent coke build up.

In an embodiment or in combination with any of the embodiments mentionedherein, all or a portion of the furnace coil or coils 324 passingthrough in the convection section 310 may be oriented horizontally,while all, or at least a portion of, the portion of the furnace coilpassing through the radiant section 322 may be oriented vertically. Inan embodiment or in combination with any of the embodiments mentionedherein, a single furnace coil may run through both the convection andradiant section. Alternatively, at least one coil may split into two ormore tubes at one or more points within the furnace, so that crackerstream may pass along multiple paths in parallel. For example, thecracker stream (including r-pyoil) 350 may be introduced into multiplecoil inlets in the convection zone 310, or into multiple tube inlets inthe radiant 320 or cross-over sections 330. When introduced intomultiple coil or tube inlets simultaneously, or nearly simultaneously,the amount of r-pyoil introduced into each coil or tube may not beregulated. In an embodiment or in combination with any of theembodiments mentioned herein, the r-pyoil and/or cracker stream may beintroduced into a common header, which then channels the r-pyoil intomultiple coil or tube inlets.

A single furnace can have at least 1, or at least 2, or at least 3, orat least 4, or at least 5, or at least 6, or at least 7, or at least 8or more, in each case coils. Each coil can be from 5 to 100, 10 to 75,or 20 to 50 meters in length and can include at least 1, or at least 2,or at least 3, or at least 4, or at least 5, or at least 6, or at least7, or at least 8, or at least 10, or at least 12, or at least 14 or moretubes. Tubes of a single coil may be arranged in many configurations andin an embodiment or in combination with any of the embodiments mentionedherein may be connected by one or more 180° (“U”) bends. One example ofa furnace coil 410 having multiple tubes 420 is shown in FIG. 6 .

An olefin plant can have a single cracking furnace, or it can have atleast 2, or at least 3, or at least 4, or at least 5, or at least 6, orat least 7, or at least 8 or more cracking furnaces operated inparallel. Any one or each furnace(s) may be gas cracker, or a liquidcracker, or a split furnace. In an embodiment or in combination with anyembodiment mentioned herein or in combination with any of the mentionedembodiments, the furnace is a gas cracker receiving a cracker feedstream containing at least 50 wt. %, or at least 75 wt. %, or at least85 wt. % or at least 90 wt. % ethane, propane, LPG, or a combinationthereof through the furnace, or through at least one coil in a furnace,or through at least one tube in the furnace, based on the weight of allcracker feed to the furnace. In an embodiment or in combination with anyembodiment mentioned herein or in combination with any of the mentionedembodiments, the furnace is a liquid or naphtha cracker receiving acracker feed stream containing at least 50 wt. %, or at least 75 wt. %,or at least 85 wt. % liquid (when measured at 25° C. and 1 atm)hydrocarbons having a carbon number from C₅-C₂₂. through the furnace, orthrough at least one coil in a furnace, or through at least one tube inthe furnace, based on the weight of all cracker feed to the furnace. Inan embodiment or in combination with any embodiment mentioned herein orin combination with any of the mentioned embodiments, the cracker is asplit furnace receiving a cracker feed stream containing at least 50 wt.%, or at least 75 wt. %, or at least 85 wt. % or at least 90 wt. %ethane, propane, LPG, or a combination thereof through the furnace, orthrough at least one coil in a furnace, or through at least one tube inthe furnace, and receiving a cracker feed stream containing at least 0.5wt. %, or at least 0.1 wt. %, or at least 1 wt. %, or at least 2 wt. %,or at least 5 wt. %, or at least 7 wt. %, or at least 10 wt. %, or atleast 13 wt. %, or at least 15 wt. %, or at least 20 wt. % liquid and/orr-pyoil (when measured at 25° C. and 1 atm), each based on the weight ofall cracker feed to the furnace.

Turning now to FIG. 7 , several possible locations for introducing ther-pyoil containing feed stream and the non-recycle cracker feed streaminto a cracking furnace are shown.

In an embodiment or in combination with any of the embodiments mentionedherein, an r-pyoil containing feed stream 550 may be combined with thenon-recycle cracker feed 552 upstream of the convection section to forma combined cracker feed stream 554, which may then be introduced intothe convection section 510 of the furnace. Alternatively, or inaddition, the r-pyoil containing feed 550 may be introduced into a firstfurnace coil, while the non-recycle cracker feed 552 is introduced intoa separate or second furnace coil, within the same furnace, or withinthe same convection zone. Both streams may then travel in parallel withone another through the convection section 510 within a convection box512, cross-over 530, and radiant section 520 within a radiant box 522,such that each stream is substantially fluidly isolated from the otherover most, or all, of the travel path from the inlet to the outlet ofthe furnace. The pyoil stream introduced into any heating zone withinthe convection section 510 can flow through the convection section 510and flow through as a vaporized stream 514 b into the radiant box 522.In other embodiments, the r-pyoil containing feed stream 550 may beintroduced into the non-recycle cracker stream 552 as it passes througha furnace coil in the convection section 510 flowing into the cross-oversection 530 of the furnace to form a combined cracker stream 514 a, asalso shown in FIG. 7 .

In an embodiment or in combination with any embodiment mentioned hereinor in combination with any of the mentioned embodiments, the r-pyoil 550may be introduced into the first furnace coil, or an additional amountintroduced into the second furnace coil, at either a first heating zoneor a second heating zone as shown in FIG. 7 . The r-pyoil 550 may beintroduced into the furnace coil at these locations through a nozzle. Aconvenient method for introducing the feed of r-pyoil is through one ormore dilution steam feed nozzles that are used to feed steam into thecoil in the convection zone. The service of one or more dilution steamnozzles may be employed to inject r-pyoil, or a new nozzle can befastened to the coil dedicated to the injection of the r-pyoil. In anembodiment or in combination with any embodiment mentioned herein or incombination with any of the mentioned embodiments, both steam andr-pyoil can be co-fed through a nozzle into the furnace coil downstreamof the inlet to the coil and upstream of a crossover, optionally at thefirst or second heating zone within the convection zone as shown in FIG.7 .

The non-recycle cracker feed stream may be mostly liquid and have avapor fraction of less than 0.25 by volume, or less than 0.25 by weight,or it may be mostly vapor and have a vapor fraction of at least 0.75 byvolume, or at least 0.75 by weight, when introduced into the furnaceand/or when combined with the r-pyoil containing feed. Similarly, ther-pyoil containing feed may be mostly vapor or mostly liquid whenintroduced into the furnace and/or when combined with the non-recyclecracker stream.

In an embodiment or in combination with any of the embodiments mentionedherein, at least a portion or all of the r-pyoil stream or cracker feedstream may be preheated prior to being introduced into the furnace. Asshown in FIG. 8 , the preheating can be performed with an indirect heatexchanger 618 heated by a heat transfer media (such as steam, hotcondensate, or a portion of the olefin-containing effluent) or via adirect fired heat exchanger 618. The preheating step can vaporize all ora portion of the stream comprising r-pyoil and may, for example,vaporize at least 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 99 weightpercent of the stream comprising r-pyoil.

The preheating, when performed, can increase the temperature of ther-pyoil containing stream to a temperature that is within about 50, 45,40, 35, 30, 25, 20, 15, 10, 5, or 2° C. of the bubble point temperatureof the r-pyoil containing stream. Additionally, or in the alternative,the preheating can increase the temperature of the stream comprisingr-pyoil to a temperature at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50,55, 60, 65, 70, 75, 80, 85, 90, or 100° C. below the coking temperatureof the stream. In an embodiment or in combination with any of theembodiments mentioned herein, the preheated r-pyoil stream can have atemperature of at least 200, 225, 240, 250, or 260° C. and/or not morethan 375, 350, 340, 330, 325, 320, or 315° C., or at least 275, 300,325, 350, 375, or 400° C. and/or not more than 600, 575, 550, 525, 500,or 475° C. When the atomized liquid (as explained below) is injectedinto the vapor phase, heated cracker stream, the liquid may rapidlyevaporate such that, for example, the entire combined cracker stream isvapor (e.g., 100 percent vapor) within 5, 4, 3, 2, or 1 second afterinjection.

In an embodiment or in combination with any of the embodiments mentionedherein, the heated r-pyoil stream (or cracker stream comprising ther-pyoil and the non-recycle cracker stream) can optionally be passedthrough a vapor-liquid separator to remove any residual heavy or liquidcomponents, when present. The resulting light fraction may then beintroduced into the cracking furnace, alone or in combination with oneor more other cracker streams as described in various embodimentsherein. For example, in an embodiment or in combination with any of theembodiments mentioned herein, the r-pyoil stream can comprise at least1, 2, 5, 8, 10, or 12 weight percent C15 and heavier components. Theseparation can remove at least 50, 55, 60, 65, 70, 75, 80, 85, 90, 95,or 99 weight percent of the heavier components from the r-pyoil stream.

Turning back to FIG. 7 , the cracker feed stream (either alone or whencombined with the r-pyoil feed stream) may be introduced into a furnacecoil at or near the inlet of the convection section. The cracker streammay then pass through at least a portion of the furnace coil in theconvection section 510, and dilution steam may be added at some point inorder to control the temperature and cracking severity in the furnace.In an embodiment or in combination with any of the embodiments mentionedherein, the steam may be added upstream of or at the inlet to theconvection section, or it may be added downstream of the inlet to theconvection section—either in the convection section, at the cross-oversection, or upstream of or at the inlet to the radiant section.Similarly, the stream comprising the r-pyoil and the non-recycle crackerstream (alone or combined with the steam) may also be introduced into orupstream or at the inlet to the convection section, or downstream of theinlet to the convection section—either within the convection section, atthe cross-over, or at the inlet to the radiant section. The steam may becombined with the r-pyoil stream and/or cracker stream and the combinestream may be introduced at one or more of these locations, or the steamand r-pyoil and/or non-recycle cracker stream may be added separately.

When combined with steam and fed into or near the cross-over section ofthe furnace, the r-pyoil and/or cracker stream can have a temperature of500, 510, 520, 530, 540, 550, 560, 570, 580, 590, 600, 610, 620, 630,640, 650, 660, 670, or 680° C. and/or not more than 850, 840, 830, 820,810, 800, 790, 780, 770, 760, 750, 740, 730, 720, 710, 705, 700, 695,690, 685, 680, 675, 670, 665, 660, 655, or 650° C. The resulting steamand r-pyoil stream can have a vapor fraction of at least 0.75, 0.80,0.85, 0.90, or at least 0.95 by weight, or at least 0.75, 0.80, 0.85,0.90, and 0.95 by volume.

When combined with steam and fed into or near the inlet to theconvection section 510, the r-pyoil and/or cracker stream can have atemperature of at least 30, 35, 40, 45, 50, 55, 60, or 65 and/or notmore than 100, 90, 80, 70, 60, 50, or 45° C.

The amount of steam added may depend on the operating conditions,including feed type and desired product, but can be added to achieve asteam-to-hydrocarbon ratio can be at least 0.10:1, 0.15:1, 0.20:1,0.25:1, 0.27:1, 0.30:1, 0.32:1, 0.35:1, 0.37:1, 0.40:1, 0.42:1, 0.45:1,0.47:1, 0.50:1, 0.52:1, 0.55:1, 0.57:1, 0.60:1, 0.62:1, 0.65:1 and/ornot more than about 1:1. 0.95:1, 0.90:1, 0.85:1, 0.80:1, 0.75:1, 0.72:1,0.70:1, 0.67:1, 0.65:1, 0.62:1, 0.60:1, 0.57:1, 0.55:1, 0.52:1, 0.50:1,or it can be in the range of from 0.1:1 to 1.0:1, 0.15:1 to 0.9:1, 0.2:1to 0.8:1, 0.3:1 to 0.75:1, or 0.4:1 to 0.6:1. When determining the“steam-to-hydrocarbon” ratio, all hydrocarbon components are includedand the ratio is by weight. In an embodiment or in combination with anyof the embodiments mentioned herein, the steam may be produced usingseparate boiler feed water/steam tubes heated in the convection sectionof the same furnace (not shown in FIG. 7 ). Steam may be added to thecracker feed (or any intermediate cracker stream within the furnace)when the cracker stream has a vapor fraction of 0.60 to 0.95, or 0.65 to0.90, or 0.70 to 0.90.

When the r-pyoil containing feed stream is introduced into the crackingfurnace separately from a non-recycle feed stream, the molar flow rateof the r-pyoil and/or the r-pyoil containing stream may be differentthan the molar flow rate of the non-recycle feed stream. In oneembodiment or in combination with any other mentioned embodiment, thereis provided a method for making one or more olefins by:

-   -   (a) feeding a first cracker stream having r-pyoil to a first        tube inlet in a cracker furnace;    -   (b) feeding a second cracker stream containing, or predominately        containing C₂ to C₄ hydrocarbons to a second tube inlet in the        cracker furnace, wherein said second tube is separate from said        first tube and the total molar flow rate of the first cracker        stream fed at the first tube inlet is lower than the total molar        flow rate of the second cracker stream to the second tube inlet,        calculated without the effect of steam. The feeding of step (a)        and step (b) can be to respective coil inlets.

For example, the molar flow rate of the r-pyoil or the first crackerstream as it passes through a tube in the cracking furnace may be atleast 5, 7, 10, 12, 15, 17, 20, 22, 25, 27, 30, 35, 40, 45, 50, 55, or60 percent lower than the flow rate of the hydrocarbon components (e.g.,C₂-C₄ or C₅-C₂₂) components in the non-recycle feed stream, or thesecond cracker stream, passing through another or second tube. Whensteam is present in both the r-pyoil containing stream, or first crackerstream, and in the second cracker stream or the non-recycle feed stream,the total molar flow rate of the r-pyoil containing stream, or firstcracker stream, (including r-pyoil and dilution steam) may be at least5, 7, 10, 12, 15, 17, 20, 22, 25, 27, 30, 35, 40, 45, 50, 55, or 60percent higher than the total molar flow rate (including hydrocarbon anddilution steam) of the non-recycle cracker feedstock, or second crackerstream (wherein the percentage is calculated as the difference betweenthe two molar flow rates divided by the flow rate of the non-recyclestream).

In an embodiment or in combination with any of the embodiments mentionedherein, the molar flow rate of the r-pyoil in the r-pyoil containingfeed stream (first cracker stream) within the furnace tube may be atleast 0.01, 0.02, 0.025, 0.03, 0.035 and/or not more than 0.06, 0.055,0.05, 0.045 kmol-lb/hr lower than the molar flow rate of the hydrocarbon(e.g., C₂-C₄ or C₅-C₂₂) in the non-recycle cracker stream (secondcracker stream). In an embodiment or in combination with any of theembodiments mentioned herein, the molar flow rates of the r-pyoil andthe cracker feed stream may be substantially similar, such that the twomolar flow rates are within 0.005, 0.001, or 0.0005 kmol-lb/hr of oneanother. The molar flow rate of the r-pyoil in the furnace tube can beat least 0.0005, 0.001, 0.0025, 0.005, 0.01, 0.02, 0.03, 0.04, 0.05,0.06, 0.07, 0.08, 0.09, 0.10, 0.11, 0.12, 0.13, 0.14, or 0.15 kilomoles-pound per hour (kmol-lb/hr) and/or not more than 0.25, 0.24, 0.23,0.22, 0.21, 0.20, 0.19, 0.18, 0.17, 0.16, 0.15, 0.14, 0.13, 0.08, 0.05,0.025, 0.01, or 0.008 kmol-lb/hr, while the molar flow rate of thehydrocarbon components in the other coil or coils can be at least 0.02,0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.11, 0.12, 0.13, 0.14,0.15, 0.16, 0.17, 0.18 and/or not more than 0.30, 0.29, 0.28, 0.27,0.26, 0.25, 0.24, 0.23, 0.22, 0.21, 0.20, 0.19, 0.18, 0.17, 0.16, 0.15kmol-lb/hr.

In an embodiment or in combination with any of the embodiments mentionedherein, the total molar flow rate of the r-pyoil containing stream(first cracker stream) can be at least 0.01, 0.02, 0.03, 0.04, 0.05,0.06, 0.07, 0.08, 0.09 and/or not more than 0.30, 0.25, 0.20, 0.15,0.13, 0.10, 0.09, 0.08, 0.07, or 0.06 kmol-lb/hr lower than the totalmolar flow rate of the non-recycle feed stream (second cracker stream),or the same as the total molar flow rate of the non-recycle feed stream(second cracker stream). The total molar flow rate of the r-pyoilcontaining stream (first cracker stream) can be at least 0.01, 0.02,0.03, 0.04, 0.05, 0.06, 0.07 and/or not more than 0.10, 0.09, 0.08,0.07, or 0.06 kmol-lb/hr higher than the total molar flow rate of thesecond cracker stream, while the total molar flow rate of thenon-recycle feed stream (second cracker stream) can be at least 0.20,0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29, 0.30, 0.31, 0.32,0.33 and/or not more than 0.50, 0.49, 0.48, 0.47. 0.46, 0.45, 0.44,0.43, 0.42, 0.41, 0.40 kmol-lb/hr.

In an embodiment or in combination with any of the embodiments mentionedherein, the r-pyoil containing stream, or first cracker stream, has asteam-to-hydrocarbon ratio that is at least 5, 10, 15, 20, 25, 30, 35,40, 45, 50, 55, 60, 65, 70, 75, or 80 percent different than thesteam-to-hydrocarbon ratio of the non-recycle feed stream, or secondcracker stream. The steam-to-hydrocarbon ratio can be higher or lower.For example, the steam-to-hydrocarbon ratio of the r-pyoil containingstream or first cracker stream can be at least 0.01, 0.025, 0.05, 0.075,0.10, 0.125, 0.15, 0.175, or 0.20 and/or not more than 0.3, 0.27, 0.25,0.22, or 0.20 different than the steam-to-hydrocarbon ratio of thenon-recycle feed stream or second cracker stream. Thesteam-to-hydrocarbon ratio of the r-pyoil containing stream or firstcracker stream can be at least 0.3, 0.32, 0.35, 0.37, 0.4, 0.42, 0.45,0.47, 0.5 and/or not more than 0.7, 0.67, 0.65, 0.62, 0.6, 0.57, 0.55,0.52, or 0.5, and the steam-to-hydrocarbon ratio of the non-recyclecracker feed or second cracker stream can be at least 0.02, 0.05, 0.07,0.10, 0.12, 0.15, 0.17, 0.20, 0.25 and/or not more than 0.45, 0.42,0.40, 0.37, 0.35, 0.32, or 0.30.

In an embodiment or in combination with any embodiments mentionedherein, the temperature of the r-pyoil containing stream as it passesthrough a cross-over section in the cracking furnace can be differentthan the temperature of the non-recycle cracker feed as it passesthrough the cross-over section, when the streams are introduced into andpassed through the furnace separately. For example, the temperature ofthe r-pyoil stream as it passes through the cross-over section may be atleast 0.01, 0.5, 1, 1.5, 2, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55,60, 65, 70, or 75 percent different than the temperature of thenon-recycle hydrocarbon stream (e.g., C₂-C₄ or C₅-C₂₂) passing throughthe cross-over section in another coil. The percentage can be calculatedbased on the temperature of the non-recycle stream according to thefollowing formula:

[(temperature of r-pyoil stream−temperature of non-recycle crackerstream)]/(temperature of non-recycle cracker steam), expressed as apercentage.

The difference can be higher or lower. The average temperature of ther-pyoil containing stream at the cross-over section can be at least 400,425, 450, 475, 500, 525, 550, 575, 580, 585, 590, 595, 600, 605, 610,615, 620, or 625° C. and/or not more than 705, 700, 695, 690, 685, 680,675, 670, 665, 660, 655, 650, 625, 600, 575, 550, 525, or 500° C., whilethe average temperature of the non-recycle cracker feed can be at least401, 426, 451, 476, 501, 526, 551, 560, 565, 570, 575, 580, 585, 590,595, 600, 605, 610, 615, 620, or 625° C. and/or not more than 705, 700,695, 690, 685, 680, 675, 670, 665, 660, 655, 650, 625, 600, 575, 550,525, or 500° C.

The heated cracker stream, which usually has a temperature of at least500, 510, 520, 530, 540, 550, 560, 570, 580, 590, 600, 610, 620, 630,640, 650, 660, 670, or 680° C. and/or not more than 850, 840, 830, 820,810, 800, 790, 780, 770, 760, 750, 740, 730, 720, 710, 705, 700, 695,690, 685, 680, 675, 670, 665, 660, 655, or 650° C., or in the range offrom 500 to 710° C., 620 to 740° C., 560 to 670° C., or 510 to 650° C.,may then pass from the convection section of the furnace to the radiantsection via the cross-over section.

In an embodiment or in combination with any of the embodiments mentionedherein, the r-pyoil containing feed stream may be added to the crackerstream at the cross-over section. When introduced into the furnace inthe cross-over section, the r-pyoil may be at least partially vaporizedby, for example, preheating the stream in a direct or indirect heatexchanger. When vaporized or partially vaporized, the r-pyoil containingstream has a vapor fraction of at least 0.5, 0.55, 0.6, 0.65, 0.7, 0.75,0.8, 0.85, 0.9, 0.95, or 0.99 by weight, or in one embodiment or incombination with any mentioned embodiments, by volume.

When the r-pyoil containing stream is atomized prior to entering thecross-over section, the atomization can be performed using one or moreatomizing nozzles. The atomization can take place within or outside thefurnace. In an embodiment or in combination with any of the embodimentsmentioned herein, an atomizing agent may be added to the r-pyoilcontaining stream during or prior to its atomization. The atomizingagent can include steam, or it may include predominantly ethane,propane, or combinations thereof. When used the atomizing agent may bepresent in the stream being atomized (e.g., the r-pyoil containingcomposition) in an amount of at least 1, 2, 4, 5, 8, 10, 12, 15, 10, 25,or 30 weight percent and/or not more than 50, 45, 40, 35, 30, 25, 20,15, or 10 weight percent.

The atomized or vaporized stream of r-pyoil may then be injected into orcombined with the cracker stream passing through the cross-over section.At least a portion of the injecting can be performed using at least onespray nozzle. At least one of the spray nozzles can be used to injectthe r-pyoil containing stream into the cracker feed stream may beoriented to discharge the atomized stream at an angle within about 45,50, 35, 30, 25, 20, 15, 10, 5, or 0° from the vertical. The spray nozzleor nozzles may also be oriented to discharge the atomized stream into acoil within the furnace at an angle within about 30, 25, 20, 15, 10, 8,5, 2, or 1° of being parallel, or parallel, with the axial centerline ofthe coil at the point of introduction. The step of injecting theatomized r-pyoil may be performed using at least two, three, four, five,six or more spray nozzles, in the cross-over and/or convection sectionof the furnace.

In an embodiment or in combination with any embodiments mentionedherein, atomized r-pyoil can be fed, alone or in combination with an atleast partially non-recycle cracker stream, into the inlet of one ormore coils in the convection section of the furnace. The temperature ofsuch an atomization can be at least 30, 35, 40, 45, 50, 55, 60, 65, 70,75, or 80° C. and/or not more than 120, 110, 100, 90, 95, 80, 85, 70,65, 60, or 55° C.

In an embodiment or in combination with any embodiments mentionedherein, the temperature of the atomized or vaporized stream can be atleast 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 75, 100, 125, 150, 175,200, 225, 250, 275, 300, 325, 350° C. and/or not more than 550, 525,500, 475, 450, 425, 400, 375, 350, 325, 300, 275, 250, 225, 200, 175,150, 125, 100, 90, 80, 75, 70, 60, 55, 50, 45, 40, 30, or 25° C. coolerthan the temperature of the cracker stream to which it is added. Theresulting combined cracker stream comprises a continuous vapor phasewith a discontinuous liquid phase (or droplets or particles) dispersedtherethrough. The atomized liquid phase may comprise r-pyoil, while thevapor phase may include predominantly C₂-C₄ components, ethane, propane,or combinations thereof. The combined cracker stream may have a vaporfraction of at least 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, or 0.99 by weight,or in one embodiment or in combination with any mentioned embodiments,by volume.

The temperature of the cracker stream passing through the cross-oversection can be at least 500, 510, 520, 530, 540, 550, 555, 560, 565,570, 575, 580, 585, 590, 595, 600, 605, 610, 615, 620, 625, 630, 635,640, 645, 650, 660, 670, or 680° C. and/or not more than 850, 840, 830,820, 810, 800, 795, 790, 785, 780, 775, 770, 765, 760, 755, 750, 745,740, 735, 730, 725, 720, 715, 710, 705, 700, 695, 690, 685, 680, 675,670, 665, 660, 655, 650, 645, 640, 635, or 630° C., or in the range offrom 620 to 740° C., 550 to 680° C., 510 to 630° C.

The resulting cracker feed stream then passes into the radiant section.In an embodiment or in combination with any of the embodiments mentionedherein, the cracker stream (with or without the r-pyoil) from theconvection section may be passed through a vapor-liquid separator toseparate the stream into a heavy fraction and a light fraction beforecracking the light fraction further in the radiant section of thefurnace. One example of this is illustrated in FIG. 8 .

In an embodiment or in combination with any of the embodiments mentionedherein, the vapor-liquid separator 640 may comprise a flash drum, whilein other embodiments it may comprise a fractionator. As the stream 614passes through the vapor-liquid separator 640, a gas stream impinges ona tray and flows through the tray, as the liquid from the tray fall toan underflow 642. The vapor-liquid separator may further comprise ademister or chevron or other device located near the vapor outlet forpreventing liquid carry-over into the gas outlet from the vapor-liquidseparator 640.

Within the convection section 610, the temperature of the cracker streammay increase by at least 50, 75, 100, 150, 175, 200, 225, 250, 275, or300° C. and/or not more than about 650, 600, 575, 550, 525, 500, 475,450, 425, 400, 375, 350, 325, 300, or 275° C., so that the passing ofthe heated cracker stream exiting the convection section 610 through thevapor-liquid separator 640 may be performed at a temperature of least400, 425, 450, 475, 500, 525, 550, 575, 600, 625, 650° C. and/or notmore than 800, 775, 750, 725, 700, 675, 650, 625° C. When heaviercomponents are present, at least a portion or nearly all of the heavycomponents may be removed in the heavy fraction as an underflow 642. Atleast a portion of the light fraction 644 from the separator 640 may beintroduced into the cross-over section or the radiant zone tubes 624after the separation, alone or in combination with one or more othercracker streams, such as, for example, a predominantly C₅-C₂₂hydrocarbon stream or a C₂-C₄ hydrocarbon stream.

Referencing FIGS. 5 and 6 , the cracker feed stream (either thenon-recycle cracker feed stream or when combined with the r-pyoil feedstream) 350 and 650 may be introduced into a furnace coil at or near theinlet of the convection section. The cracker feed stream may then passthrough at least a portion of the furnace coil in the convection section310 and 610, and dilution steam 360 and 660 may be added at some pointin order to control the temperature and cracking severity in the radiantsection 320 and 620. The amount of steam added may depend on the furnaceoperating conditions, including feed type and desired productdistribution, but can be added to achieve a steam-to-hydrocarbon ratioin the range of from 0.1 to 1.0, 0.15 to 0.9, 0.2 to 0.8, 0.3 to 0.75,or 0.4 to 0.6, calculated by weight. In an embodiment or in combinationwith any of the embodiments mentioned herein, the steam may be producedusing separate boiler feed water/steam tubes heated in the convectionsection of the same furnace (not shown in FIG. 5 ). Steam 360 and 660may be added to the cracker feed (or any intermediate cracker feedstream within the furnace) when the cracker feed stream has a vaporfraction of 0.60 to 0.95, or 0.65 to 0.90, or 0.70 to 0.90 by weight, orin one embodiment or in combination with any mentioned embodiments, byvolume.

The heated cracker stream, which usually has a temperature of at least500, or at least 510, or at least 520, or at least 530, or at least 540,or at least 550, or at least 560, or at least 570, or at least 580, orat least 590, or at least 600, or at least 610, or at least 620, or atleast 630, or at least 640, or at least 650, or at least 660, or atleast 670, or at least 680, in each case ° C. and/or not more than 850,or not more than 840, or not more than 830, or not more than 820, or notmore than 810, or not more than 800, or not more than 790, or not morethan 780, or not more than 770, or not more than 760, or not more than750, or not more than 740, or not more than 730, or not more than 720,or not more than 710, or not more than 705, or not more than 700, or notmore than 695, or not more than 690, or not more than 685, or not morethan 680, or not more than 675, or not more than 670, or not more than665, or not more than 660, or not more than 655, or not more than 650,in each case ° C., or in the range of from 500 to 710° C., 620 to 740°C., 560 to 670° C., or 510 to 650° C., may then pass from the convectionsection 610 of the furnace to the radiant section 620 via the cross-oversection 630. In an embodiment or in combination with any of theembodiments mentioned herein, the r-pyoil containing feed stream 550 maybe added to the cracker stream at the cross-over section 530 as shown inFIG. 6 . When introduced into the furnace in the cross-over section, ther-pyoil may be at least partially vaporized or atomized prior to beingcombined with the cracker stream at the cross-over. The temperature ofthe cracker stream passing through the cross-over 530 or 630 can be atleast 400, 425, 450, 475, or at least 500, or at least 510, or at least520, or at least 530, or at least 540, or at least 550, or at least 560,or at least 570, or at least 580, or at least 590, or at least 600, orat least 610, or at least 620, or at least 630, or at least 640, or atleast 650, or at least 660, or at least 670, or at least 680, in eachcase ° C. and/or not more than 850, or not more than 840, or not morethan 830, or not more than 820, or not more than 810, or not more than800, or not more than 790, or not more than 780, or not more than 770,or not more than 760, or not more than 750, or not more than 740, or notmore than 730, or not more than 720, or not more than 710, or not morethan 705, or not more than 700, or not more than 695, or not more than690, or not more than 685, or not more than 680, or not more than 675,or not more than 670, or not more than 665, or not more than 660, or notmore than 655, or not more than 650, in each case ° C., or in the rangeof from 620 to 740° C., 550 to 680° C., 510 to 630° C.

The resulting cracker feed stream then passes through the radiantsection, wherein the r-pyoil containing feed stream is thermally crackedto form lighter hydrocarbons, including olefins such as ethylene,propylene, and/or butadiene. The residence time of the cracker feedstream in the radiant section can be at least 0.1, or at least 0.15, orat least 0.2, or at least 0.25, or at least 0.3, or at least 0.35, or atleast 0.4, or at least 0.45, in each case seconds and/or not more than2, or not more than 1.75, or not more than 1.5, or not more than 1.25,or not more than 1, or not more than 0.9, or not more than 0.8, or notmore than 0.75, or not more than 0.7, or not more than 0.65, or not morethan 0.6, or not more than 0.5, in each case seconds. The temperature atthe inlet of the furnace coil is at least 500, or at least 510, or atleast 520, or at least 530, or at least 540, or at least 550, or atleast 560, or at least 570, or at least 580, or at least 590, or atleast 600, or at least 610, or at least 620, or at least 630, or atleast 640, or at least 650, or at least 660, or at least 670, or atleast 680, in each case ° C. and/or not more than 850, or not more than840, or not more than 830, or not more than 820, or not more than 810,or not more than 800, or not more than 790, or not more than 780, or notmore than 770, or not more than 760, or not more than 750, or not morethan 740, or not more than 730, or not more than 720, or not more than710, or not more than 705, or not more than 700, or not more than 695,or not more than 690, or not more than 685, or not more than 680, or notmore than 675, or not more than 670, or not more than 665, or not morethan 660, or not more than 655, or not more than 650, in each case ° C.,or in the range of from 550 to 710° C., 560 to 680° C., or 590 to 650°C., or 580 to 750° C., 620 to 720° C., or 650 to 710° C.

The coil outlet temperature can be at least 640, or at least 650, or atleast 660, or at least 670, or at least 680, or at least 690, or atleast 700, or at least 720, or at least 730, or at least 740, or atleast 750, or at least 760, or at least 770, or at least 780, or atleast 790, or at least 800, or at least 810, or at least 820, in eachcase ° C. and/or not more than 1000, or not more than 990, or not morethan 980, or not more than 970, or not more than 960, or not more than950, or not more than 940, or not more than 930, or not more than 920,or not more than 910, or not more than 900, or not more than 890, or notmore than 880, or not more than 875, or not more than 870, or not morethan 860, or not more than 850, or not more than 840, or not more than830, in each case ° C., in the range of from 730 to 900° C., 750 to 875°C., or 750 to 850° C.

The cracking performed in the coils of the furnace may include crackingthe cracker feed stream under a set of processing conditions thatinclude a target value for at least one operating parameter. Examples ofsuitable operating parameters include, but are not limited to maximumcracking temperature, average cracking temperature, average tube outlettemperature, maximum tube outlet temperature, and average residencetime. When the cracker stream further includes steam, the operatingparameters may include hydrocarbon molar flow rate and total molar flowrate. When two or more cracker streams pass through separate coils inthe furnace, one of the coils may be operated under a first set ofprocessing conditions and at least one of the other coils may beoperated under a second set or processing conditions. At least onetarget value for an operating parameter from the first set of processingconditions may differ from a target value for the same parameter in thesecond set of conditions by at least 0.01, 0.03, 0.05, 0.1, 0.25, 0.5,1, 2, 5, 7, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80,85, 90, or 95 percent and/or not more than about 95, 90, 85, 80, 75, 70,65, 60, 55, 50, 45, 40, 35, 30, 25, 20, or 15 percent. Examples include0.01 to 30, 0.01 to 20, 0.01 to 15, 0.03 to 15 percent. The percentageis calculated according to the following formula:

[(measured value for operating parameter)−(target value for operatingparameter]/[(target value for operating parameter)], expressed as apercentage.

As used herein, the term “different,” means higher or lower.

The coil outlet temperature can be at least 640, 650, 660, 670, 680,690, 700, 720, 730, 740, 750, 760, 770, 780, 790, 800, 810, 820° C.and/or not more than 1000, 990, 980, 970, 960, 950, 940, 930, 920, 910,900, 890, 880, 875, 870, 860, 850, 840, 830° C., in the range of from730 to 900° C., 760 to 875° C., or 780 to 850° C.

In an embodiment or in combination with any of the embodiments mentionedherein, the addition of r-pyoil to a cracker feed stream may result inchanges to one or more of the above operating parameters, as compared tothe value of the operating parameter when an identical cracker feedstream is processed in the absence of r-pyoil. For example, the valuesof one or more of the above parameters may be at least 0.01, 0.03, 0.05,0.1, 0.25, 0.5, 1, 2, 5, 7, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60,65, 70, 75, 80, 85, 90, or 95 percent different (e.g., higher or lower)than the value for the same parameter when processing an identical feedstream without r-pyoil, ceteris paribus. The percentage is calculatedaccording to the following formula:

[(measured value for operating parameter)−(target value for operatingparameter]/[(target value for operating parameter)], expressed as apercentage.

One example of an operating parameter that may be adjusted with theaddition of r-pyoil to a cracker stream is coil outlet temperature. Forexample, in an embodiment or in combination with any embodimentmentioned herein, the cracking furnace may be operated to achieve afirst coil outlet temperature (COT1) when a cracker stream having nor-pyoil is present. Next, r-pyoil may be added to the cracker stream,via any of the methods mentioned herein, and the combined stream may becracked to achieve a second coil outlet temperature (COT2) that isdifferent than COT1.

In some cases, when the r-pyoil is heavier than the cracker stream, COT2may be less than COT1, while, in other case, when the r-pyoil is lighterthan the cracker stream, COT2 may be greater than or equal to COT1. Whenthe r-pyoil is lighter than the cracker stream, it may have a 50%boiling point that is at least 5, 10, 15, 20, 25, 30, 35, 40, 45, or 50and/or not more than 80, 75, 70, 65, 60, 55, or 50 percent higher thanthe 50% boiling point of the cracker stream. The percentage iscalculated according to the following formula:

[(50% boiling point of r-pyoil in ° R)−(50% boiling point of crackerstream)]/[(50% boiling point of cracker stream)], expressed as apercentage.

Alternatively, or in addition, the 50% boiling point of the r-pyoil maybe at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75,80, 85, 90, 95, or 100° C. and/or not more than 300, 275, 250, 225, or200° C. lower than the 50% boiling point of the cracker stream. Heaviercracker streams can include, for example, vacuum gas oil (VGO),atmospheric gas oil (AGO), or even coker gas oil (CGO), or combinationsthereof.

When the r-pyoil is lighter than the cracker stream, it may have a 50%boiling point that is at least 5, 10, 15, 20, 25, 30, 35, 40, 45, or 50and/or not more than 80, 75, 70, 65, 60, 55, or 50 percent lower thanthe 50% boiling point of the cracker stream. The percentage iscalculated according to the following formula:

[(50% boiling point of r-pyoil)−(50% boiling point of crackerstream)]/[(50% boiling point of cracker stream)], expressed as apercentage.

Additionally, or in the alternative, the 50% boiling point of ther-pyoil may be at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60,65, 70, 75, 80, 85, 90, 95, or 100° C. and/or not more than 300, 275,250, 225, or 200° C. higher than the 50% boiling point of the crackerstream. Lighter cracker streams can include, for example, LPG, naphtha,kerosene, natural gasoline, straight run gasoline, and combinationsthereof.

In some cases, COT1 can be at least 5, 10, 15, 20, 25, 30, 35, 40, 45,50° C. and/or not more than about not more than 150, 140, 130, 125, 120,110, 105, 100, 90, 80, 75, 70, or 65° C. different (higher or lower)than COT2, or COT1 can be at least 0.3, 0.6, 1, 2, 5, 10, 15, 20, or 25and/or not more than 80, 75, 70, 65, 60, 50, 45, or 40 percent differentthan COT2 (with the percentage here defined as the difference betweenCOT1 and COT2 divided by COT1, expressed as a percentage). At least oneor both of COT1 and COT2 can be at least 730, 750, 77, 800, 825, 840,850, 860, 870, 880, 890, 900, 910, 920, 930, 940, 950, 960, 970, 980,990 and/or not more than 1200, 1175, 1150, 1140, 1130, 1120, 1110, 1100,1090, 1080, 1070, 1060, 1050, 1040, 1030, 1020, 1010, 1000, 990, 980,970, 960 950, 940, 930, 920, 910, or 900° C.

In an embodiment or in combination with any of the embodiments mentionedherein, the mass velocity of the cracker feed stream through at leastone, or at least two radiant coils (for clarity as determine across theentire coil as opposed to a tube within a coil) is in the range of 60 to165 kilograms per second (kg/s) per square meter (m2) of cross-sectionalarea (kg/s/m2), 60 to 130 (kg/s/m2), 60 to 110 (kg/s/m2), 70 to 110(kg/s/m2), or 80 to 100 (kg/s/m2). When steam is present, the massvelocity is based on the total flow of hydrocarbon and steam.

In one embodiment or in combination with any mentioned embodiments,there is provided a method for making one or more olefins by:

-   -   (a) cracking a cracker stream in a cracking unit at a first coil        outlet temperature (COT1);    -   (b) subsequent to step (a), adding a stream comprising a recycle        content pyrolysis oil composition (r-pyoil) to said cracker        stream to form a combined cracker stream; and    -   (c) cracking said combined cracker stream in said cracking unit        at a second coil outlet temperature (COT2), wherein said second        coil outlet temperature is lower, or at least 3° C. lower, or at        least 5° C. lower than said first coil outlet temperature.

The reason or cause for the temperature drop in the second coil outlettemperature (COT2) is not limited, provided that COT2 is lower than thefirst coil outlet temperature (COT1). In one embodiment or incombination with any mentioned embodiments, In one embodiment or incombination with any other mentioned embodiments, the COT2 temperatureon the r-pyoil fed coils can be set to a temperature that lower than, orat least 1, 2, 3, 4, or at least 5° C. lower than COT1 (“Set” Mode), orit can be allowed to change or float without setting the temperature onthe r-pyoil fed coils (“Free Float” Mode”).

The COT2 can be set at least 5° C. lower than COT1 in a Set Mode. Allcoils in a furnace can be r-pyoil containing feed streams, or at least1, or at least two of the coils can be r-pyoil containing feed streams.In either case, at least one of the r-pyoil containing coils can be in aSet Mode. By reducing the cracking severity of the combined crackingstream, one can take advantage of the lower heat energy required tocrack r-pyoil when it has an average number average molecular weightthat is higher than the cracker feed stream, such as a gaseous C2-C4feed. While the cracking severity on the cracker feed (e.g. C2-C4) canbe reduced and thereby increase the amount of unconverted C2-C4 feed ina single pass, the higher amount of unconverted feed (e.g. C2-C4 feed)is desirable to increase the ultimate yield of olefins such as ethyleneand/or propylene through multiple passes by recycling the unconvertedC2-C4 feed through the furnace. Optionally, other cracker products, suchas the aromatic and diene content, can be reduced.

In one embodiment or in combination with any mentioned embodiments, theCOT2 in a coil can be fixed in a Set Mode to be lower than, or at least1, 2, 3, 4, or at least 5° C. lower than the COT1 when the hydrocarbonmass flow rate of the combined cracker stream in at least one coil isthe same as or less than the hydrocarbon mass flow rate of the crackerstream in step (a) in said coil. The hydrocarbon mass flow rate includesall hydrocarbons (cracker feed and if present the r-pyoil and/or naturalgasoline or any other types of hydrocarbons) and other than steam.Fixing the COT2 is advantageous when the hydrocarbon mass flow rate ofthe combined cracker stream in step (b) is the same as or less than thehydrocarbon mass flow rate of the cracker stream in step (a) and thepyoil has a higher average molecular weight than the average molecularweight of the cracker stream. At the same hydrocarbon mass flow rates,when pyoil has a heavier average molecular weight than the crackerstream, the COT2 will tend to rise with the addition of pyoil becausethe higher molecular weight molecules require less thermal energy tocrack. If one desires to avoid overcracking the pyoil, the lowered COT2temperature can assist to reduce by-product formation, and while theolefin yield in the singe pass is also reduced, the ultimate yield ofolefins can be satisfactory or increased by recycling unconvertedcracker feed through the furnace.

In a Set Mode, the temperature can be fixed or set by adjusting thefurnace fuel rate to burners.

In one embodiment or in combination with any other mentionedembodiments, the COT2 is in a Free Float Mode and is as a result offeeding pyoil and allowing the COT2 to rise or fall without fixing atemperature to the pyoil fed coils. In this embodiment, not all of thecoils contain r-pyoil. The heat energy supplied to the r-pyoilcontaining coils can be supplied by keeping constant temperature on, orfuel feed rate to the burners on the non-recycle cracker feed containingcoils. Without fixing or setting the COT2, the COT2 can be lower thanCOT1 when pyoil is fed to the cracker stream to form a combined crackerstream that has a higher hydrocarbon mass flow rate than the hydrocarbonmass flow rate of the cracker stream in step (a). Pyoil added to acracker feed to increase the hydrocarbon mass flow rate of the combinedcracker feed lowers the COT2 and can outweigh the temperature riseeffect of using a higher average molecular weight pyoil. These effectscan be seen while other cracker conditions are held constant, such asthe dilution steam ratio, feed locations, composition of the crackerfeed and pyoil, and fuel feed rates to the firebox burners in thefurnace on the tubes containing only cracker feed and no feed ofr-pyoil.

The COT2 can be lower than, or at least 1, 2, 3, 4, 5, 8, 10, 12, 15,18, 20, 25, 30, 35, 40, 45, 50° C. and/or not more than about not morethan 150, 140, 130, 125, 120, 110, 105, 100, 90, 80, 75, 70, or 65° C.lower than COT1.

Independent of the reason or cause of the temperature drop in COT2, thetime period for engaging step (a) is flexible, but ideally, step (a)reaches a steady state before engaging step (b). In one embodiment or incombination with any mentioned embodiments, step (a) is in operation forat least 1 week, or at least 2 weeks, or at least 1 month, or at least 3months, or at least 6 months, or at least 1 year, or at least 1.5 years,or at least 2 years. The step (a) can be represented by a crackerfurnace in operation that has never accepted a feed of pyoil or acombined feed of cracker feed and pyoil. Step (b) can be the first timea furnace has accepted a feed of pyoil or a combined cracker feedcontaining pyoil. In one embodiment or in combination with any othermentioned embodiments, steps (a) and (b) can be cycled multiple timesper year, such as at least 2×/yr, or at least 3×/yr, or at least 4×/yr,or at least 5×/yr, or at least 6×/yr, or at least 8×/yr, or at least12×/yr, as measured on a calendar year. Campaigning a feed of pyoil isrepresentative of multiple cycling of steps (a) and (b). When the feedsupply of pyoil is exhausted or shut off, the COT1 is allowed to reach asteady state temperature before engaging step (b).

Alternatively, the feed of pyoil to a cracker feed can be continuousover the entire course of at least 1 calendar year, or at least 2calendar years.

In one embodiment or in combination with any other mentionedembodiments, the cracker feed composition used in steps (a) and (b)remains unchanged, allowing for regular compositional variationsobserved during the course of a calendar year. In one embodiment or incombination with any other mentioned embodiments, the flow of crackerfeed in step (a) is continuous and remains continuous as pyoil is to thecracker feed to make a combined cracker feed. The cracker feed in steps(a) and (b) can be drawn from the same source, such as the sameinventory or pipeline.

In one embodiment or in combination with any mentioned embodiments, theCOT2 is lower than, or at least 1, 2, 3, 4, or at least 5° C. lower forat least 30% of the time that the pyoil is fed to the cracker stream toform the combined cracker stream, or at least 40% of the time, or atleast 50% of the time, or at least 60% of the time, or at least 70% ofthe time, or at least 80% of the time, or at least 85% of the time, orat least 90% of the time, or at least 95% of the time, the time measuredas when all conditions, other than COT's, are held constant, such ascracker and pyoil feed rates, steam ratio, feed locations, compositionof the cracker feed and pyoil, etc.

In one embodiment or in combination with any mentioned embodiments, thehydrocarbon mass flow rate of combined cracker feed can be increased.There is now provided a method for making one or more olefins by:

-   -   (a) cracking a cracker stream in a cracking unit at a first        hydrocarbon mass flow rate (MF1);    -   (b) subsequent to step (a), adding a stream comprising a recycle        content pyrolysis oil composition (r-pyoil) to said cracker        stream to form a combined cracker stream having a second        hydrocarbon mass flow rate (MF2) that is higher than MF1; and    -   (c) cracking said combined cracker stream at MF2 in said        cracking unit to obtain an olefin-containing effluent that has a        combined output of ethylene and propylene that same as or higher        than the output of ethylene and propylene obtained by cracking        only said cracker stream at MF1.

The output refers to the production of the target compounds in weightper unit time, for example, kg/hr. Increasing the mass flow rate of thecracker stream by addition of r-pyoil can increase the output ofcombined ethylene and propylene, thereby increasing the throughput ofthe furnace. Without being bound to a theory, it is believed that thisis made possible because the total energy of reaction is not asendothermic with the addition of pyoil relative to total energy ofreaction with a lighter cracker feed such as propane or ethane. Sincethe heat flux on the furnace is limited and the total heat of reactionof pyoil is less endothermic, more of the limited heat energy becomesavailable to continue cracking the heavy feed per unit time. The MF2 canbe increased by at least 1, 2, 3, 4, 5, 7, 10, 10, 13, 15, 18, or 20%through a r-pyoil fed coil, or can be increased by at least 1, 2, 3, 5,7, 10, 10, 13, 15, 18, or 20% as measured by the furnace output providedthat at least one coil processes r-pyoil. Optionally, the increase incombined output of ethylene and propylene can be accomplished withoutvarying the heat flux in the furnace, or without varying the r-pyoil fedcoil outlet temperature, or without varying the fuel feed rate to theburners assigned to heat the coils containing only non-recycle contentcracker feed, or without varying the fuel feed rate to any of theburners in the furnace. The MF2 higher hydrocarbon mass flow rate in ther-pyoil containing coils can be through one or at least one coil in afurnace, or two or at least two, or 50% or at least 50%, or 75% or atleast 75%, or through all of the coils in a furnace.

The olefin-containing effluent stream can have a total output ofpropylene and ethylene from the combined cracker stream at MF2 that isthe same as or higher than the output of propylene and ethylene of aneffluent stream obtained by cracking the same cracker feed but withoutr-pyoil by at least 0.5%, or at least 1%, or at least 2%, or at least2.5%, determined as:

${\%{increase}} = {\frac{{{Omf}2} - {{Omf}1}}{{Omf}1} \times 100}$

-   -   where O_(mf1) is the combined output of propylene and ethylene        content in the cracker effluent at MF1 made without r-pyoil; and    -   O_(mf2) is the combined output of propylene and ethylene content        in the cracker effluent at MF2 made with r-pyoil.

The olefin-containing effluent stream can have a total output ofpropylene and ethylene from the combined cracker stream at MF2 that isleast 1, 5, 10, 15, 20%, and/or up to 80, 70, 65% of the mass flow rateincrease between MF2 and MF1 on a percentage basis. Examples of suitableranges include 1 to 80, or 1 to 70, or 1 to 65, or 5 to 80, or 5 to 70,or 5 to 65, or 10 to 80, or 10 to 70, or 10 to 65, or 15 to 80, or 15 to70, or 15 to 65, or 20 to 80, or 20 to 70, or 20 to 65, or 25 to 80, or25 to 70, or 26 to 65, or 35 to 80, or 35 to 70, or 35 to 65, or 40 to80, or 40 to 70, or 40 to 65, each expressed as a percent %. Forexample, if the percentage difference between MF2 and MF1 is 5%, and thetotal output of propylene and ethylene is increased by 2.5%, the olefinincrease as a function of mass flow increase is 50% (2.5%/5%×100). Thiscan be determined as:

${\%{relative}{increase}} = {\frac{{\Delta O}\%}{{\Delta{MF}}\%} \times 100}$

-   -   where ΔO % is percentage increase between the combined output of        propylene and ethylene content in the cracker effluent at MF1        made without r-pyoil and MF2 made with r-pyoil (using the        aforementioned equation); and ΔMF % is the percentage increase        of MF2 over MF1.

Optionally, the olefin-containing effluent stream can have a total wt. %of propylene and ethylene from the combined cracker stream at MF2 thatis the same as or higher than the wt. % of propylene and ethylene of aneffluent stream obtained by cracking the same cracker feed but withoutr-pyoil by at least 0.5%, or at least 1%, or at least 2%, or at least2.5%, determined as:

${\%{increase}} = {\frac{{{Emf}2} - {{Emf}1}}{{Emf}1} \times 100}$

-   -   where E_(mf1) is the combined wt. % of propylene and ethylene        content in the cracker effluent at MF1 made without r-pyoil; and    -   E_(mf2) is the combined wt. % of propylene and ethylene content        in the cracker effluent at MF2 made with r-pyoil.

There is also provided a method for making one or more olefins, saidmethod comprising:

-   -   (a) cracking a cracker stream in a cracking furnace to provide a        first olefin-containing effluent exiting the cracking furnace at        a first coil outlet temperature (COT1);    -   (b) subsequent to step (a), adding a stream comprising a recycle        content pyrolysis oil composition (r-pyoil) to said cracker        stream to form a combined cracker stream; and    -   (c) cracking said combined cracker stream in said cracking unit        to provide a second olefin-containing effluent exiting the        cracking furnace at a second coil outlet temperature (COT2),

wherein, when said r-pyoil is heavier than said cracker stream, COT2 isequal to or less than COT1,

wherein, when said r-pyoil is lighter than said cracker stream, COT2 isgreater than or equal to COT1.

In this method, the embodiments described above for a COT2 lower thanCOT1 are also applicable here. The COT2 can be in a Set Mode or FreeFloat Mode. In one embodiment or in combination with any other mentionedembodiments, the COT2 is in a Free Float Mode and the hydrocarbon massflow rate of the combined cracker stream in step (b) is higher than thehydrocarbon mass flow rate of the cracker stream in step (a). In oneembodiment or in combination with any mentioned embodiments, the COT2 isin a Set Mode.

In one embodiment or in combination with any mentioned embodiments,there is provided a method for making one or more olefins by:

-   -   (a) cracking a cracker stream in a cracking unit at a first coil        outlet temperature (COT1);    -   (b) subsequent to step (a), adding a stream comprising a recycle        content pyrolysis oil composition (r-pyoil) to said cracker        stream to form a combined cracker stream; and    -   (c) cracking said combined cracker stream in said cracking unit        at a second coil outlet temperature (COT2), wherein said second        coil outlet temperature is higher than the first coil outlet        temperature.

The COT2 can be at least 5, 8, 10, 12, 15, 18, 20, 25, 30, 35, 40, 45,50° C. and/or not more than about not more than 150, 140, 130, 125, 120,110, 105, 100, 90, 80, 75, 70, or 65° C. higher than COT1.

In one embodiment or in combination with any other mentionedembodiments, r-pyoil is added to the inlet of at least one coil, or atleast two coils, or at least 50%, or at least 75%, or all of the coils,to form at least one combined cracker stream, or at least two combinedcracker streams, or at least the same number of combined crackersstreams as coils accepting a feed of r-pyoil. At least one, or at leasttwo of the combined cracker streams, or at least all of the r-pyoil fedcoils can have a COT2 that is higher than their respective COT1. In oneembodiment or in combination with any mentioned embodiments, at leastone, or at least two coils, or at least 50%, or at least 75% of thecoils within said cracking furnace contain only non-recycle contentcracker feed, with at least one of the coils in the cracking furnacebeing fed with r-pyoil, and the coil or at least some of multiple coilsfed with r-pyoil having a COT2 higher than their respective COT1.

In one embodiment or in combination with any mentioned embodiments, thehydrocarbon mass flow rate of the combined stream in step (b) issubstantially the same as or lower than the hydrocarbon mass flow rateof the cracker stream in step (a). By substantially the same is meantnot more than a 2% difference, or not more than a 1% difference, or notmore than a 0.25% difference. When the hydrocarbon mass flow rate of thecombined cracker stream in step (b) is substantially the same as orlower than the hydrocarbon mass flow rate of the cracker stream (a), andthe COT2 is allowed to operate in a Free Float Mode (where at least 1 ofthe tubes contains non-recycle content cracker stream), the COT2 on ther-pyoil containing coil can rise relative to COT1. This is the case eventhough the pyoil, having a larger number average molecular weightcompared to the cracker stream, requires less energy to crack. Withoutbeing bound to a theory, it is believed that one or a combination offactors contribute to the temperature rise, including the following:

-   -   (i) lower heat energy is required to crack pyoil in the combined        stream and/or    -   (ii) the occurrence of exothermic reactions among cracked        products of pyoil, such as diels-alder reactions.

This effect can be seen when the other process variables are constant,such as the firebox fuel rate, dilution steam ratio, location of feeds,and composition of the cracker feed.

In one embodiment or in combination with any mentioned embodiments, theCOT2 can be set or fixed to a higher temperature than COT1 (the SetMode). This is more applicable when the hydrocarbon mass flow rate ofthe combined cracker stream is higher than the hydrocarbon mass flowrate of the cracker stream which would otherwise lower the COT2. Thehigher second coil outlet temperature (COT2) can contribute to anincreased severity and a decreased output of unconverted lighter crackerfeed (e.g. C2-C4 feed), which can assist with downstream capacityrestricted fractionation columns.

In one embodiment or in combination with any mentioned embodiments,whether the COT2 is higher or lower than COT1, the cracker feedcompositions are the same when a comparison is made between COT2 with aCOT1. Desirably, the cracker feed composition in step (a) is the samecracker composition as used to make the combined cracker stream in step(b). Optionally, the cracker composition feed in step (a) iscontinuously fed to the cracker unit, and the addition of pyoil in step(b) is to the continuous cracker feed in step (a). Optionally, the feedof pyoil to the cracker feed is continuous for at least 1 day, or atleast 2 days, or at least 3 days, or at least 1 week, or at least 2weeks, or at least 1 month, or at least 3 months, or at least 6 monthsor at least 1 year.

The amount of raising or lowering the cracker feed in step (b) in any ofthe mentioned embodiments can be at least 2%, or at least 5%, or atleast 8%, or at least 10%. In one embodiment or in combination with anymentioned embodiments, the amount of lowering the cracker feed in step(b) can be an amount that corresponds to the addition of pyoil byweight. In one embodiment or in combination with any mentionedembodiments, the mass flow of the combined cracker feed is at least 1%,or at least 5%, or at least 8%, or at least 10% higher than thehydrocarbon mass flow rate of the cracker feed in step (a).

In any or all of the mentioned embodiments, the cracker feed or combinedcracker feed mass flows and COT relationships and measurements aresatisfied if any one coil in the furnace satisfies the statedrelationships but can also be present in multiple tubes depending on howthe pyoil is fed and distributed.

In an embodiment or in combination with any of the embodiments mentionedherein, the burners in the radiant zone provide an average heat fluxinto the coil in the range of from 60 to 160 kW/m2 or 70 to 145 kW/m2 or75 to 130 kW/m2. The maximum (hottest) coil surface temperature is inthe range of 1035 to 1150° C. or 1060 to 1180° C. The pressure at theinlet of the furnace coil in the radiant section is in the range of 1.5to 8 bar absolute (bara), or 2.5 to 7 bara, while the outlet pressure ofthe furnace coil in the radiant section is in the range of from 1.03 to2.75 bara, or 1.03 to 2.06 bara. The pressure drop across the furnacecoil in the radiant section can be from 1.5 to 5 bara, or 1.75 to 3.5bara, or 1.5 to 3 bara, or 1.5 to 3.5 bara.

In an embodiment or in combination with any of the embodiments mentionedherein, the yield of olefin—ethylene, propylene, butadiene, orcombinations thereof—can be at least 15, or at least 20, or at least 25,or at least 30, or at least 35, or at least 40, or at least 45, or atleast 50, or at least 55, or at least 60, or at least 65, or at least70, or at least 75, or at least 80, in each case percent. As usedherein, the term “yield” refers to the mass of product/mass offeedstock×100%. The olefin-containing effluent stream comprises at leastabout 30, or at least 40, or at least 50, or at least 60, or at least70, or at least 75, or at least 80, or at least 85, or at least 90, orat least 95, or at least 97, or at least 99, in each case weight percentof ethylene, propylene, or ethylene and propylene, based on the totalweight of the effluent stream.

In an embodiment or in combination with one or more embodimentsmentioned herein, the olefin-containing effluent stream 670 can compriseC₂ to C₄ olefins, or propylene, or ethylene, or C₄ olefins, in an amountof at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75,80, 85, or 90 weight percent, based on the weight of theolefin-containing effluent. The stream may comprise predominantlyethylene, predominantly propylene, or predominantly ethylene andpropylene, based on the olefins in the olefin-containing effluent, orbased on the weight of the C₁-C₅ hydrocarbons in the olefin-containingeffluent, or based on the weight of the olefin-containing effluentstream. The weight ratio of ethylene-to-propylene in theolefin-containing effluent stream can be at least about 0.2:1, 0.3:1,0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1, 1.1:1, 1.2:1, 1.3:1,1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, or 2:1 and/or not more than3:1, 2.9:1, 2.8:1, 2.7:1, 2.5:1, 2.3:1, 2.2:1, 2.1:1, 2:1, 1.7:1, 1.5:1,or 1.25:1. In an embodiment or in combination with one or moreembodiments mentioned herein, the olefin-containing effluent stream canhave a ratio of propylene:ethylene that is higher than thepropylene:ethylene ratio of an effluent stream obtained by cracking thesame cracker feed but without r-pyoil at equivalent dilution steamratios, feed locations, cracker feed compositions (other than ther-pyoil), and allowing the coils fed with r-pyoil to be in the FloatMode, or if all coils in a furnace are fed with r-pyoil, then at thesame temperature prior to feeding r-pyoil. As discussed above, this ispossible when the mass flow of the cracker feed remains substantiallythe same resulting in a higher hydrocarbon mass flow rate of thecombined cracker stream when r-pyoil is added relative to the originalfeed of the cracker stream.

The olefin-containing effluent stream can have a ratio ofpropylene:ethylene that is at least 1% higher, or at least 2% higher, orat least 3% higher, or at least 4% higher, or at least 5% higher or atleast 7% higher or at least 10% higher or at least 12% higher or atleast 15% higher or at least 17% higher or at least 20% higher than thepropylene:ethylene ratio of an effluent stream obtained by cracking thesame cracker feed but without r-pyoil. Alternatively or in addition, theolefin-containing effluent stream can have a ratio of propylene:ethylenethat is up to 50% higher, or up to 45% higher, or up to 40% higher, orup to 35% higher, or up to 25% higher, or up to 20% higher than thepropylene:ethylene ratio of an effluent stream obtained by cracking thesame cracker feed but without r-pyoil, in each case determined as:

${\%{increase}} = {\frac{{Er} - E}{E} \times 100}$

-   -   where E is the propylene:ethylene ratio by wt. % in the cracker        effluent made without r-pyoil; and    -   E_(r) is the propylene:ethylene ratio by wt. % in the cracker        effluent made with r-pyoil.

In an embodiment or in combination with any of the embodiments mentionedherein, the amount of ethylene and propylene can remain substantiallyunchanged or increased in the cracked olefin-containing effluent streamrelative to an effluent stream without r-pyoil. It is surprising that aliquid r-pyoil can be fed to a gas fed furnace that accepts and cracks apredominant C₂-C₄ composition and obtain an olefin-containing effluentstream that can remain substantially unchanged or improved in certaincases relative to a C₂-C₄ cracker feed without r-pyoil. The heavymolecular weight of r-pyoil could have predominately contributed to theformation of aromatics and participate in the formation of olefins(ethylene and propylene in particular) in only a minor amount. However,we have found that the combined weight percent of ethylene andpropylene, and even the output, does not significantly drop, and in manycases stays the same or can increase when r-pyoil is added to a crackerfeed to form a combined cracker feed at the same hydrocarbon mass flowrates relative to a cracker feed without r-pyoil. The olefin-containingeffluent stream can have a total wt. % of propylene and ethylene that isthe same as or higher than the propylene and ethylene content of aneffluent stream obtained by cracking the same cracker feed but withoutr-pyoil by at least 0.5%, or at least 1%, or at least 2%, or at least2.5%, determined as:

${\%{increase}} = {\frac{{Er} - E}{E} \times 100}$

-   -   where E is the combined wt. % of propylene and ethylene content        in the cracker effluent made without r-pyoil; and    -   E_(r) is the combined wt. % of propylene and ethylene content in        the cracker effluent made with r-pyoil.

In an embodiment or in combination with one or more embodimentsmentioned herein, the wt. % of propylene can improve in anolefin-containing effluent stream when the dilution steam ratio (ratioof steam:hydrocarbons by weight) is above 0.3, or above 0.35, or atleast 0.4. The increase in the wt. % of propylene when the dilutionsteam ratio is at least 0.3, or at least 0.35, or at least 0.4 can be upto 0.25 wt. %, or up to 0.4 wt. %, or up to 0.5 wt. %, or up to 0.7 wt.%, or up to 1 wt. %, or up to 1.5 wt. %, or up to 2 wt. %, where theincrease is measured as the simple difference between the wt. % ofpropylene between an olefin-containing effluent stream made with r-pyoilat a dilution steam ratio of 0.2 and an olefin-containing effluentstream made with r-pyoil at a dilution steam ratio of at least 0.3, allother conditions being the same.

When the dilution steam ratio is increased as noted above, the ratio ofpropylene:ethylene can also increase, or can be at least 1% higher, orat least 2% higher, or at least 3% higher, or at least 4% higher, or atleast 5% higher or at least 7% higher or at least 10% higher or at least12% higher or at least 15% higher or at least 17% higher or at least 20%higher than the propylene:ethylene ratio of an olefin-containingeffluent stream made with r-pyoil at a dilution steam ratio of 0.2.

In an embodiment or in combination with one or more embodimentsmentioned herein, when the dilution steam ratio is increased, theolefin-containing effluent stream can have a reduced wt. % of methane,when measured relative to an olefin-containing effluent stream at adilution steam ratio of 0.2. The wt. % of methane in theolefin-containing effluent stream can be reduced by at least 0.25 wt. %,or by at least 0.5 wt. %, or by at least 0.75 wt. %, or by at least 1wt. %, or by at least 1.25 wt. %, or by at least 1.5 wt. %, measured asthe absolute value difference in wt. % between the olefin-containingeffluent stream at a dilution steam ratio of 0.2 and at the higherdilution steam ratio value.

In an embodiment or in combination with one or more embodimentsmentioned herein, the amount of unconverted products in theolefin-containing effluent is decreased, when measured relative to acracker feed that does not contain r-pyoil and all other conditionsbeing the same, including hydrocarbon mass flow rate. For example, theamount of propane and/or ethane can be decreased by addition of r-pyoil.This can be advantageous to decrease the mass flow of the recycle loopto thereby (a) decrease cryogenic energy costs and/or (b) potentiallyincrease capacity on the plant if the plant is already capacityconstrained. Further it can debottleneck the propylene fractionator ifit is already to its capacity limit. The amount of unconverted productsin the olefin containing effluent can decrease by at least 2%, or atleast 5%, or at least 8%, or at least 10%, or at least 13%, or at least15%, or at least 18%, or at least 20%.

In an embodiment or in combination with one or more embodimentsmentioned herein, the amount of unconverted products (e.g. combinedpropane and ethane amount) in the olefin-containing effluent isdecreased while the combined output of ethylene and propylene does notdrop and is even improved, when measured relative to a cracker feed thatdoes not contain r-pyoil. Optionally, all other conditions are the sameincluding the hydrocarbon mass flow rate and with respect totemperature, where the fuel feed rate to heat the burners to thenon-recycle content cracker fed coils remains unchanged, or optionallywhen the fuel feed rate to all coils in the furnace remains unchanged.Alternatively, the same relationship can hold true on a wt. % basisrather than an output basis.

For example, the combined amount (either or both of output or wt. %) ofpropane and ethane in the olefin containing effluent can decrease by atleast 2%, or at least 5%, or at least 8%, or at least 10%, or at least13,%, or at least 15%, or at least 18%, or at least 20%, and in eachcase up to 40% or up to 35% or up to 30%, in each case without adecrease in the combined amount of ethylene and propylene, and even canaccompany an increase in the combined amount of ethylene and propylene.In another example, the amount of propane in the olefin containingeffluent can decrease by at least 2%, or at least 5%, or at least 8%, orat least 10%, or at least 13,%, or at least 15%, or at least 18%, or atleast 20%, and in each case up to 40% or up to 35% or up to 30%, in eachcase without a decrease in the combined amount of ethylene andpropylene, and even can accompany an increase in the combined amount ofethylene and propylene. In any one of these embodiments, the crackerfeed (other than r-pyoil and as fed to the inlet of the convection zone)can be predominately propane by moles, or at least 90 mole % propane, orat least 95 mole % propane, or at least 96 mole % propane, or at least98 mole % propane; or the fresh supply of cracker feed can be at leastHD5 quality propane.

In an embodiment or in combination with one or more embodimentsmentioned herein, the ratio of propane:(ethylene and propylene) in theolefin-containing effluent can decrease with the addition of r-pyoil tothe cracker feed when measured relative to the same cracker feed withoutpyoil and all other conditions being the same, measured either as wt. %or output. The ratio of propane:(ethylene and propylene combined) in theolefin-containing effluent can be not more than 0.50:1, or less than0.50:1, or not more than 0.48:1, or not more than 0.46:1, or no morethan 0.43:1, or no more than 0.40:1, or no more than 0.38:1, or no morethan 0.35:1, or no more than 0.33:1, or no more than 0.30:1. The lowratios indicate that a high amount of ethylene+propylene can be achievedor maintained with a corresponding drop in unconverted products such aspropane.

In an embodiment or in combination with one or more embodimentsmentioned herein, the amount of C₆₊ products in the olefin-containingeffluent can be increased, if such products are desired such as for aBTX stream to make derivates thereof, when r-pyoil and steam are feddownstream of the inlet to the convection box, or when one or both ofr-pyoil and steam are fed at the cross-over location. The amount of C₆₊products in the olefin-containing effluent can be increased by 5%, or by10%, or by 15%, or by 20%, or by 30% when r-pyoil and steam are feddownstream of the inlet to the convection box, when measured againstfeeding r-pyoil at the inlet to the convection box, all other conditionsbeing the same. The % increase can be calculated as:

${\%{increase}} = {\frac{{Ei} - {Ed}}{Ei} \times 100}$

-   -   where E_(i) is the C₆₊ content in the olefin-containing cracker        effluent made by introducing r-pyoil at the inlet of the        convection box; and    -   E_(d) is the C₆₊ content in the olefin-containing cracker        effluent made by introducing r-pyoil and steam downstream of the        inlet of the convection box.

In an embodiment or in combination with any of the embodiments mentionedherein, the cracked olefin-containing effluent stream may includerelatively minor amounts of aromatics and other heavy components. Forexample, the olefin-containing effluent stream may include at least 0.5,1, 2, or 2.5 weight percent and/or not more than about 20, 19, 18, 17,16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, or 1 weight percentof aromatics, based on the total weight of the stream. We have foundthat the level of C₆₊ species in the olefin-containing effluent can benot more than 5 wt. %, or not more than 4 wt. %, or not more than 3.5wt. %, or not more than 3 wt. %, or not more than 2.8 wt. %, or not morethan 2.5 wt. %. The C₆₊ species includes all aromatics, as well as allparaffins and cyclic compounds having a carbon number of 6 or more. Asused throughout, the mention of amounts of aromatics can be representedby amounts of C₆₊ species since the amount of aromatics would not exceedthe amount of C₆₊ species.

The olefin-containing effluent may have an olefin-to-aromatic ratio, byweight %, of at least 2:1, 3.1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1,11:1, 12:1, 13:1, 14:1, 15:1, 16:1, 17:1, 18:1, 19:1, 20:1, 21:1, 22:1,23:1, 24:1, 25:1, 26:1, 27:1, 28:1, 29:1, or 30:1 and/or not more than100:1, 90:1, 85:1, 80:1, 75:1, 70:1, 65:1, 60:1, 55:1, 50:1, 45:1, 40:1,35:1, 30:1, 25:1, 20:1, 15:1, 10:1, or 5:1. As used herein,“olefin-to-aromatic ratio” is the ratio of total weight of C2 and C3olefins to the total weight of aromatics, as defined previously. In anembodiment or in combination with any of the embodiments mentionedherein, the effluent stream can have an olefin-to-aromatic ratio of atleast 2.5:1, 2.75:1, 3.5:1, 4.5:1, 5.5:1, 6.5:1, 7.5:1, 8.5:1, 9.5:1,10.5:1, 11.5:1, 12.5:1, or 13:5:1.

The olefin-containing effluent may have an olefin:C₆₊ ratio, by weight%, of at least 8.5:1, or at least 9.5:1, or at least 10:1, or at least10.5:1, or at least 12:1, or at least 13:1, or at least 15:1, or atleast 17:1, or at least 19:1, or at least 20:1, or at least 25:1, orleast 28:1, or at least 30:1. In addition or in the alternative, theolefin-containing effluent may have an olefin:C₆₊ ratio of up to 40:1,or up to 35:1, or up to 30:1, or up to 25:1, or up to 23:1. As usedherein, “olefin-to-aromatic ratio” is the ratio of total weight of C2and C3 olefins to the total weight of aromatics, as defined previously.

Additionally, or in the alternative, the olefin-containing effluentstream can have an olefin-to-C6+ ratio of at least about 1.5:1, 1.75:1,2:1, 2.25:1, 2.5:1, 2.75:1, 3:1, 3.25:1, 3.5:1, 3.75:1, 4:1, 4.25:1,4.5:1, 4.75:1, 5:1, 5.25:1, 5.5:1, 5.75:1, 6:1, 6.25:1, 6.5:1, 6.75:1,7:1, 7.25:1, 7.5:1, 7.75:1, 8:1, 8.25:1, 8.5:1, 8.75:1, 9:1, 9.5:1,10:1, 10.5:1, 12:1, 13:1, 15:1, 17:1, 19:1, 20:1, 25:1, 28:1, or 30:1.

In an embodiment or in combination with any of the embodiments mentionedherein, the olefin:aromatic ratio decreases with an increase in theamount of r-pyoil added to the cracker feed. Since r-pyoil cracks at alower temperature, it will crack earlier than propane or ethane, andtherefore has more time to react to make other products such asaromatics. Although the aromatic content in the olefin-containingeffluent increases with an increasing amount of pyoil, the amount ofaromatics produced is remarkably low as noted above.

The olefin-containing composition may also include trace amounts ofaromatics. For example, the composition may have a benzene content of atleast 0.25, 0.3, 0.4, 0.5 weight percent and/or not more than about 2,1.7, 1.6, 1.5 weight percent. Additionally, or in the alternative, thecomposition may have a toluene content of at least 0.005, 0.010, 0.015,or 0.020 and/or not more than 0.5, 0.4, 0.3, or 0.2 weight percent. Bothpercentages are based on the total weight of the composition.Alternatively, or in addition, the effluent can have a benzene contentof at least 0.2, 0.3, 0.4, 0.5, or 0.55 and/or not more than about 2,1.9, 1.8, 1.7, or 1.6 weight percent and/or a toluene content of atleast 0.01, 0.05, or 0.10 and/or not more than 0.5, 0.4, 0.3, or 0.2weight percent.

In an embodiment or in combination with any of the embodiments mentionedherein, the olefin-containing effluent withdrawn from a cracking furnacewhich has cracked a composition comprising r-pyoil may include anelevated amount of one or more compounds or by-products not found inolefin-containing effluent streams formed by processing conventionalcracker feed. For example, the cracker effluent formed by crackingr-pyoil (r-olefin) may include elevated amounts of 1,3-butadiene,1,3-cyclopentadiene, dicyclopentadiene, or a combination of thesecomponents. In an embodiment or in combination with any of theembodiments mentioned herein, the total amount (by weight) of thesecomponents may be at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55,60, 65, 70, 75, 80, or 85 percent higher than an identical cracker feedstream processed under the same conditions and at the same mass feedrate, but without r-pyoil. The total amount (by weight) of 1,3-butadienemay be at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70,75, 80, or 85 percent higher than an identical cracker feed streamprocessed under the same conditions and at the same mass feed rate, butwithout r-pyoil. The total amount (by weight) of 1,3-cyclopentadiene maybe at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75,80, or 85 percent higher than an identical cracker feed stream processedunder the same conditions and at the same mass feed rate, but withoutr-pyoil. The total amount (by weight) of dicyclopentadiene may be atleast 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, or85 percent higher than an identical cracker feed stream processed underthe same conditions and at the same mass feed rate, but without r-pyoil.The percent difference is calculated by dividing the difference inweight percent of one or more of the above components in the r-pyoil andconventional streams by the amount (in weight percent) of the componentin the conventional stream, or:

${\%{increase}} = {\frac{{Er} - E}{E} \times 100}$

-   -   where E is the wt. % of the component in the cracker effluent        made without r-pyoil; and    -   E_(r) is the wt. % of the component in the cracker effluent made        with r-pyoil.

In an embodiment or in combination with any of the embodiments mentionedherein, the olefin-containing effluent stream may comprise acetylene.The amount of acetylene can be at least 2000 ppm, at least 5000 ppm, atleast 8000 ppm, or at least 10,000 ppm based on the total weight of theeffluent stream from the furnace. It may also be not more than 50,000ppm, not more than 40,000 ppm, not more than 30,000 ppm, or not morethan 25,000 ppm, or not more than 10,000 ppm, or not more than 6,000ppm, or not more than 5000 ppm.

In an embodiment or in combination with any of the embodiments mentionedherein, the olefin-containing effluent stream may comprise methylacetylene and propadiene (MAPD). The amount of MAPD may be at least 2ppm, at least 5 ppm, at least 10 ppm, at least 20 pm, at least 50 ppm,at least 100 ppm, at least 500 ppm, at least 1000 ppm, at least 5000ppm, or at least 10,000 ppm, based on the total weight of the effluentstream. It may also be not more than 50,000 ppm, not more than 40,000ppm, or not more than 30,000 ppm, or not more than 10,000 ppm, or notmore than 6,000 ppm, or not more than 5,000 ppm.

In an embodiment or in combination with any of the embodiments mentionedherein, the olefin-containing effluent stream may comprise low or noamounts of carbon dioxide. The olefin-containing effluent stream canhave an amount, in wt. %, of carbon dioxide that is not more than theamount of carbon dioxide in an effluent stream obtained by cracking thesame cracker feed but without r-pyoil at equivalent conditions, or anamount this is not higher than 5%, or not higher than 2% of the amountof carbon dioxide, in wt. %, or the same amount as a comparativeeffluent stream without r-pyoil. Alternatively or in addition, theolefin-containing effluent stream can have an amount of carbon dioxidethat is not more than 1000 ppm, or not more than 500 ppm, or not morethan 100 ppm, or not more than 80 ppm, or not more than 50 ppm, or notmore than 25 ppm, or not more than 10 ppm, or not more than 5 ppm.

Turning now to FIG. 9 , a block diagram illustrating the main elementsof the furnace effluent treatment section are shown.

As shown in FIG. 9 , the olefin-containing effluent stream from thecracking furnace 700, which includes recycle content) is cooled rapidly(e.g., quenched) in a transfer line exchange (“TLE”) 680 as shown inFIG. 8 in order to prevent production of large amounts of undesirableby-products and to minimize fouling in downstream equipment, and also togenerate steam. In an embodiment or in combination with any of theembodiments mentioned herein, the temperature of ther-composition-containing effluent from the furnace can be reduced by 35to 485° C., 35 to 375° C., or 90 to 550° C. to a temperature of 500 to760° C. The cooling step is performed immediately after the effluentstream leaves the furnace such as, for example, within 1 to 30, 5 to 20,or 5 to 15 milliseconds. In an embodiment or in combination with any ofthe embodiments mentioned herein, the quenching step is performed in aquench zone 710 via indirect heat exchange with high-pressure water orsteam in a heat exchanger (sometimes called a transfer line exchanger asshown in FIG. 5 as TLE 340 and FIG. 8 as TLE 680), while, in otherembodiments, the quench step is carried out by directly contacting theeffluent with a quench liquid 712 (as generally shown in FIG. 9 ). Thetemperature of the quench liquid can be at least 65, or at least 80, orat least 90, or at least 100, in each case ° C. and/or not more than210, or not more than 180, or not more than 165, or not more than 150,or not more than 135, in each case ° C. When a quench liquid is used,the contacting may occur in a quench tower and a liquid stream may beremoved from the quench tower comprising gasoline and other similarboiling-range hydrocarbon components. In some cases, quench liquid maybe used when the cracker feed is predominantly liquid, and a heatexchanger may be used when the cracker feed is predominantly vapor.

The resulting cooled effluent stream is then vapor liquid separated andthe vapor is compressed in a compression zone 720, such as in a gascompressor having, for example, between 1 and 5 compression stages withoptional inter-stage cooling and liquid removal. The pressure of the gasstream at the outlet of the first set of compression stages is in therange of from 7 to 20 bar gauge (barg), 8.5 to 18 psig (0.6˜4.3 barg),or 9.5 to 14 barg.

The resulting compressed stream is then treated in an acid gas removalzone 722 for removal of acid gases, including CO, CO2, and H2S bycontact with an acid gas removal agent. Examples of acid gas removalagents can include, but are not limited to, caustic and various types ofamines. In an embodiment or in combination with any of the embodimentsmentioned herein, a single contactor may be used, while, in otherembodiments, a dual column absorber-stripper configuration may beemployed.

The treated compressed olefin-containing stream may then be furthercompressed in another compression zone 724 via a compressor, optionallywith inter-stage cooling and liquid separation. The resulting compressedstream, which has a pressure in the range of 20 to 50 barg, 25 to 45barg, or 30 to 40 barg. Any suitable moisture removal method can be usedincluding, for example, molecular sieves or other similar process to drythe gas in a drying zone 726. The resulting stream 730 may then bepassed to the fractionation section, wherein the olefins and othercomponents may be separated in to various high-purity product orintermediate streams.

Turning now to FIG. 10 , a schematic depiction of the main steps of thefractionation section is provided. In an embodiment or in combinationwith any of the embodiments mentioned herein, the initial column of thefractionation train may not be a demethanizer 810, but may be adeethanizer 820, a depropanizer 840, or any other type of column. Asused herein, the term “demethanizer,” refers to a column whose light keyis methane. Similarly, “deethanizer,” and “depropanizer,” refer tocolumns with ethane and propane as the light key component,respectively.

As shown in FIG. 10 , a feed stream 870 from the quench section mayintroduced into a demethanizer (or other) column 810, wherein themethane and lighter (CO, CO₂, H₂) components 812 are separated from theethane and heavier components 814. The demethanizer is operated at atemperature of at least −145, or at least −142, or at least −140, or atleast −135, in each case ° C. and/or not more than −120, −125, −130,−135° C. The bottoms stream 814 from the demethanizer column, whichincludes at least 50, or at least 55, or at least 60, or at least 65, orat least 70, or at least 75, or at least 80, or at least 85, or at least90, or at least 95 or at least 99, in each case percent of the totalamount of ethane and heavier components introduced into the column, isthen introduced into a deethanizer column 820, wherein the C2 andlighter components 816 are separated from the C3 and heavier components818 by fractional distillation. The de-ethanizer 820 can be operatedwith an overhead temperature of at least −35, or at least −30, or atleast −25, or at least −20, in each case ° C. and/or not more than −5,−10, −10, −20° C., and an overhead pressure of at least 3, or at least5, or at least 7, or at least 8, or at least 10, in each case bargand/or not more than 20, or not more than 18, or not more than 17, ornot more than 15, or not more than 14, or not more than 13, in each casebarg. The deethanizer column 820 recovers at least 60, or at least 65,or at least 70, or at least 75, or at least 80, or at least 85, or atleast 90, or at least 95, or at least 97, or at least 99, in each casepercent of the total amount of C₂ and lighter components introduced intothe column in the overhead stream. In an embodiment or in combinationwith any of the embodiments mentioned herein, the overhead stream 816removed from the deethanizer column comprises at least 50, or at least55, or at least 60, or at least 65, or at least 70, or at least 75, orat least 80, or at least 85, or at least 90, or at least 95, in eachcase weight percent of ethane and ethylene, based on the total weight ofthe overhead stream.

As shown in FIG. 10 , the C₂ and lighter overhead stream 816 from thedeethanizer 820 is further separated in an ethane-ethylene fractionatorcolumn (ethylene fractionator) 830. In the ethane-ethylene fractionatorcolumn 830, an ethylene and lighter component stream 822 can bewithdrawn from the overhead of the column 830 or as a side stream fromthe top ½ of the column, while the ethane and any residual heaviercomponents are removed in the bottoms stream 824. The ethylenefractionator 830 may be operated at an overhead temperature of at least−45, or at least −40, or at least −35, or at least −30, or at least −25,or at least −20, in each case ° C. and/or not more than −15, or not morethan −20, or not more than −25, in each case ° C., and an overheadpressure of at least 10, or at least 12, or at least 15, in each casebarg and/or not more than 25, 22, 20 barg. The overhead stream 822,which is enriched in ethylene, can include at least 70, or at least 75,or at least 80, or at least 85, or at least 90, or at least 95, or atleast 97, or at least 98, or at least 99, in each case weight percentethylene, based on the total weight of the stream and may be sent todownstream processing unit for further processing, storage, or sale. Theoverhead ethylene stream 822 produced during the cracking of a crackerfeedstock containing r-pyoil is a r-ethylene composition or stream. Inan embodiment or in combination with any of the embodiments mentionedherein, the r-ethylene stream may be used to make one or morepetrochemicals.

The bottoms stream from the ethane-ethylene fractionator 824 may includeat least 40, or at least 45, or at least 50, or at least 55, or at least60, or at least 65, or at least 70, or at least 75, or at least 80, orat least 85, or at least 90, or at least 95, or at least 98, in eachcase weight percent ethane, based on the total weight of the bottomsstream. All or a portion of the recovered ethane may be recycled to thecracker furnace as additional feedstock, alone or in combination withthe r-pyoil containing feed stream, as discussed previously.

The liquid bottoms stream 818 withdrawn from the deethanizer column,which may be enriched in C3 and heavier components, may be separated ina depropanizer 840, as shown in FIG. 10 . In the depropanizer 840, C3and lighter components are removed as an overhead vapor stream 826,while C4 and heavier components may exit the column in the liquidbottoms 828. The depropanizer 840 can be operated with an overheadtemperature of at least 20, or at least 35, or at least 40, in each case° C. and/or not more than 70, 65, 60, 55° C., and an overhead pressureof at least 10, or at least 12, or at least 15, in each case barg and/ornot more than 20, or not more than 17, or not more than 15, in each casebarg. The depropanizer column 840 recovers at least 60, or at least 65,or at least 70, or at least 75, or at least 80, or at least 85, or atleast 90, or at least 95, or at least 97, or at least 99, in each casepercent of the total amount of C3 and lighter components introduced intothe column in the overhead stream 826. In an embodiment or incombination with any of the embodiments mentioned herein, the overheadstream 826 removed from the depropanizer column 840 comprises at leastor at least 50, or at least 55, or at least 60, or at least 65, or atleast 70, or at least 75, or at least 80, or at least 85, or at least90, or at least 95, or at least 98, in each case weight percent ofpropane and propylene, based on the total weight of the overhead stream826.

The overhead stream 826 from the depropanizer 840 are introduced into apropane-propylene fractionator (propylene fractionator) 860, wherein thepropylene and any lighter components are removed in the overhead stream832, while the propane and any heavier components exit the column in thebottoms stream 834. The propylene fractionator 860 may be operated at anoverhead temperature of at least 20, or at least 25, or at least 30, orat least 35, in each case ° C. and/or not more than 55, 50, 45, 40° C.,and an overhead pressure of at least 12, or at least 15, or at least 17,or at least 20, in each case barg and/or not more than 20, or not morethan 17, or not more than 15, or not more than 12, in each case barg.The overhead stream 860, which is enriched in propylene, can include atleast 70, or at least 75, or at least 80, or at least 85, or at least90, or at least 95, or at least 97, or at least 98, or at least 99, ineach case weight percent propylene, based on the total weight of thestream and may be sent to downstream processing unit for furtherprocessing, storage, or sale. The overhead propylene stream producedduring the cracking of a cracker feedstock containing r-pyoil is ar-propylene composition or stream. In an embodiment or in combinationwith any of the embodiments mentioned herein, the stream may be used tomake one or more petrochemicals.

The bottoms stream 834 from the propane-propylene fractionator 860 mayinclude at least 40, or at least 45, or at least 50, or at least 55, orat least 60, or at least 65, or at least 70, or at least 75, or at least80, or at least 85, or at least 90, or at least 95, or at least 98, ineach case weight percent propane, based on the total weight of thebottoms stream 834. All or a portion of the recovered propane may berecycled to the cracker furnace as additional feedstock, alone or incombination with r-pyoil, as discussed previously.

Referring again to FIG. 10 , the bottoms stream 828 from thedepropanizer column 840 may be sent to a debutanizer column 850 forseparating C₄ components, including butenes, butanes and butadienes,from C5+ components. The debutanizer can be operated with an overheadtemperature of at least 20, or at least 25, or at least 30, or at least35, or at least 40, in each case ° C. and/or not more than 60, or notmore than 65, or not more than 60, or not more than 55, or not more than50, in each case ° C. and an overhead pressure of at least 2, or atleast 3, or at least 4, or at least 5, in each case barg and/or not morethan 8, or not more than 6, or not more than 4, or not more than 2, ineach case barg. The debutanizer column recovers at least 60, or at least65, or at least 70, or at least 75, or at least 80, or at least 85, orat least 90, or at least 95, or at least 97, or at least 99, in eachcase percent of the total amount of C4 and lighter components introducedinto the column in the overhead stream 836. In an embodiment or incombination with any of the embodiments mentioned herein, the overheadstream 836 removed from the debutanizer column comprises at least 30, orat least 35, or at least 40, or at least 45, or at least 50, or at least55, or at least 60, or at least 65, or at least 70, or at least 75, orat least 80, or at least 85, or at least 90, or at least 95, in eachcase weight percent of butadiene, based on the total weight of theoverhead stream. The overhead stream 836 produced during the cracking ofa cracker feedstock containing r-pyoil is a r-butadiene composition orstream. The bottoms stream 838 from the debutanizer includes mainly C5and heavier components, in an amount of at least 50, or at least 60, orat least 70, or at least 80, or at least 90, or at least 95 weightpercent, based on the total weight of the stream. The debutanizerbottoms stream 838 may be sent for further separation, processing,storage, sale or use.

The overhead stream 836 from the debutanizer, or the C4s, can besubjected to any conventional separation methods such as extraction ordistillation processes to recover a more concentrated stream ofbutadiene.

The Production of Mixed Esters

In one embodiment or in combination with any of the mentionedembodiments, r-propylene and/or r-ethylene may be used (in one or morereactions) to produce at least one mixed ester. As discussed below ingreater detail, propylene can be used to produce mixed esters by: (1)subjecting the propylene to hydroformylation to produce anisobutyraldehdye; (2) hydrogenating the isobutyraldehdye to form anisobutanol; and (3) esterifying the isobutanol in the presence of anacid to form a mixed ester. Additionally or alternatively, ethylene mayalso be used to produce mixed esters by: (1a) optionally oxidizingethylene to form acetaldehyde and hydrogenating the acetaldehyde to formethanol or (1b) hydrating the ethylene to form ethanol and (2)esterifying the ethanol in the presence of an acid to form a mixedester.

In one embodiment or in combination with any of the mentionedembodiments, the r-propylene is utilized in a reaction scheme to make amixed ester. In one embodiment or in combination with any of thementioned embodiments, r-propylene is first converted to anisobutyraldehyde and this isobutyraldehyde is then converted intoisobutanol, which may then be used to produce mixed esters. In oneembodiment or in combination with any of the mentioned embodiments,“r-isobutyraldehyde” refers to isobutyraldehyde that is derived fromr-propylene and “r-isobutanol” refers to isobutanol that is derived fromr-propylene, where derived from means that at least some of thefeedstock source material (that is used in any reaction scheme to make areactant or intermediate) has some content of r-propylene.

In one embodiment or in combination with any of the mentionedembodiments, the r-ethylene is utilized in a reaction scheme to make amixed ester. In one embodiment or in combination with any of thementioned embodiments, r-ethanol may be produced from r-ethylene usingtwo alternative pathways. In the first pathway, r-ethylene may beconverted acetaldehyde and this acetaldehyde is then converted intoethanol. In the alternative pathway, r-ethylene may be hydrated directlyinto ethanol. Subsequently, the ethanol may be converted into mixedesters. In one embodiment or in combination with any of the mentionedembodiments, “r-acetaldehyde” refers to acetaldehyde that is derivedfrom r-ethylene and “r-ethanol” refers to ethanol that is derived fromr-ethylene, where derived from means that at least some of the feedstocksource material (that is used in any reaction scheme to make a reactantor intermediate) has some content of r-ethylene.

r-Mixed esters can be made starting from r-propylene which is subjectedto hydroformylation in a hydroformylation vessel to formr-isobutyraldehyde. The r-isobutyraldehyde can be subjected tohydrogenation conditions in a hydrogenation vessel to form r-isobutanol.The r-isobutanol can then be subjected to esterification conditions inan esterification vessel in the presence of an acid to form the r-mixedesters.

r-Ethylene can be used to make r-mixed esters. r-Ethylene can besubjected to oxidation Condit (i.e., Wacker Process) ons in an oxidationvessel to form r-acetaldehyde. The r-acetaldehyde can be subjected tohydrogenation conditions in a hydrogenation vessel to form r-ethanol.Alternatively, the r-ethylene can be subjected to hydration conditionsin a hydration vessel to form r-ethanol. The r-ethanol can be subjectedto esterification conditions in an esterification vessel in the presenceof an acid to from the r-mixed esters.

Referring back to the hydroformylation method staring from propylene,the hydroformylation method may be used to convert r-propylene intor-isobutyraldehyde. The r-propylene used to feed to the hydroformylationreactor can be a purified, partially purified, or impure r-propylenestream. The r-propylene can be a purified feedstock and can contain morethan 98 wt. % propylene, or at least 98.2 wt. %, or at least 98.5 wt. %,or at least 98.7 wt. %, or at least 98.9 wt. %, or at least 99.0 wt. %,or at least 99.2 wt. %, or at least 99.5 wt. %, or at least 99.7 wt. %propylene, based on the weight of r-propylene feed.

In one embodiment or in combination with any of the mentionedembodiments, a method of making a recycle content isobutyraldehydeproduct includes a hydroformylation method in which a r-propylene is fedto a reaction vessel and reacted to produce a hydroformylation effluentthat includes r-isobutyraldehyde.

Although any process for converting r-propylene to isobutyraldehyde canbe employed, the rhodium catalyzed process, or the low pressurehydroformylation process, is a desirable synthetic route in view of itshigh catalyst activity and selectivity, and low pressure and lowtemperature requirements.

More specifically, the hydroformylation process for makingr-isobutyraldehyde includes contacting propylene with syngas (H2, CO)and a catalyst complex in a reaction zone at an elevated temperature andelevated pressure for a sufficient period of time to permit reaction ofethylene with syngas to form isobutyraldehyde. Suitable methods formaking isobutyraldehyde include the high and low pressure oxo processes,in which r-propylene is hydroformylated to make isobutyraldehyde. Thehydroformylation reaction temperature can be any temperature from 50° C.to 250° C. and the reaction pressure can be from 15 psig to about 5100psig.

The hydroformylation process can be a high or low pressure process.Examples of hydroformylation reaction pressures (in the reaction zonewithin the hydroformylation reactor), or the propylene pressure fed tothe reactor, for a high pressure process, include at least 550 psig orat least 4000 psig. The pressure can be up to 5100 psig or up to 4500psig.

In the high pressure hydroformylation process, the temperature withinthe reaction zone can be at least 140° C. or at least 170° C. Inaddition, or in the alternative, the temperature can be up to 250° C. orup to 200° C.

In a low pressure process, hydroformylation reaction pressures (in thereaction zone within the hydroformylation reactor), or the propylenepressure fed to the reactor, include at least 15 psig or at least 300psig. The pressure can be less than 550 psig or up to 285 psig. Ingeneral, the reaction pressure is at least 200 psig and up to 400 psig.

In the low pressure hydroformylation process, the temperature within thereaction zone can be at least 50° C. or at least 90° C. In addition, orin the alternative, the temperature can be up to 160° C. or up to 100°C. In general, the reaction temperature is from 60° C. to 115° C.

Generally, the molar ratio of hydrogen to carbon monoxide introducedinto the reactor, which is not necessarily the syngas ratio, or in thereactor, is maintained within the range of about 0.1:1 to about 10:1, or0.5:1 to 4:1, or 0.9:1 to 4:1, or 1:1 to 4:1. In many hydroformylations,the rate of reaction as well as yield of isobutyraldehyde may beincreased by increasing the hydrogen to carbon monoxide molar ratioabove 4.0, and up to about 10.0 or more.

Suitable hydroformylation catalysts include any known to be effective tocatalyst the conversion of propylene to isobutyraldehyde. Examples ofsuch catalysts are metals complexed with ligands. Suitable metalsinclude the cobalt, rhodium, and ruthenium metals.

Conversion of the propylene molecules in the r-propylene can be at least80%, or at least 85%, or at least 90%, or at least 95%, or at least 97%,or at least 98%, or at least 99%. The yield will be the same values,given that no isomers of isobutyraldehyde exist.

The solvent employed is one which dissolves the catalyst and propyleneand does not act as a poison to the catalyst. Ideally, the solvent alsois inert with respect to the syngas and isobutyraldehyde.

A rhodium phosphine complex can be used that is water soluble or oilsoluble. Examples of suitable solvents include the various alkanes,cycloalkanes, alkenes, cycloalkenes, ethers, esters, and carbocyclicaromatic compound that are liquids at standard temperature and 1 atm.,such as pentane, dodecane, decalin, octane, iso-octane mixtures,cyclopentane, cyclohexane, cyclooctane, cyclododecane,methylcyclohexane; aromatic hydrocarbons such as benzene, toluene,ethylbenzene, xylene isomers, tetralin, cumene, naphtha,alkyl-substituted aromatic compounds such as the isomers ofdiisopropylbenzene, triisopropylbenzene and tert-butylbenzene; andalkenes and cycloalkenes such as 1,7-octadiene, dicyclopentadiene,1,5-cyclo-octadiene, octene-1, octene-2, 4-vinylcyclohexene,cyclohexene, 1,5,9-cyclododecatriene, pentene-1 and crude hydrocarbonmixtures such as mineral oils, naphtha and kerosene; and functionalsolvents such as isobutyl isobutyrate and bis(2-ethylhexyl) phthalate,2,2,4-trimethyl-1,3-pentanediol monoisobutyrate; ethers and polyetherssuch as tetrahydrofuran and tetraglyme; and desirably includes the insitu products formed during the course of the reaction such ascondensation products of aldehydes (dimers and trimers and aldolcondensation products of isobutyraldehyde) or the triorganophosphorusligand itself (e.g., oxides of the triphenylphosphine); and mixtures ofany two or more of the foregoing. The isobutyraldehyde product, otheraldehydes, and the higher boiling by-products that are formed during thehydroformylation process or separated during purification anddistillation or used in the purification/separation processes may beused as solvents. Of the listed solvents, those that have a sufficientlyhigh boiling to remain as a liquid for the most part in a reactor underthe reaction temperatures and pressures are desirable. Catalysts thatcome out of solution over time can be withdrawn from the reactor.

The r-propylene can be fed as a dedicated stream solely of r-propylene,or it can be combined with catalyst metal, ligand, carbon monoxide,hydrogen, solvent, and/or impurities carried with the r-propylenesupplied to the manufacturer of the isobutyraldehyde, as a combinedstream. Desirably, the r-propylene stream and a syngas stream arecombined and fed to the reactor as a combined stream. The amount or feedrate of r-propylene to the reaction zone of the hydroformylationreactor, along with temperature, can control the production rate to theproduct isobutyraldehyde.

In one embodiment or in combination with any of the mentionedembodiments, the hydroformylation reaction is carried out in the liquidphase, meaning that a catalyst is dissolved in a liquid and ther-propylene, carbon monoxide, and hydrogen gases contact the liquidphase, either across the top surface or desirably through the liquid. Toreduce mass transfer limitations, a high contact surface area betweenthe catalyst solution and the gas phase is desired. This can beaccomplished in a well stirred or continuously stirred tank, and bysparging the gas phases through the catalyst solution. The r-propylenegas and syngas can be sparged through the liquid medium that containsdissolved catalyst and solvent, to increase the contact surface area andresidence time between r-propylene, syngas, and catalyst.

Exemplary hydroformylation reactions and reactors that may be used aredescribed in U.S. Pat. Nos. 4,287,369, 4,287,370, 4,322,564, and4,479,012 and European Patent Application Publication Nos. EP114611A,EP103810A, and EP144745, the disclosures of which are incorporatedherein by reference in their entirety.

Like with r-propylene, the r-ethylene may also be converted into analdehyde for subsequent processes. As shown in FIG. 10 , the r-ethylenemay be subjected to an oxidation reaction (i.e., the Wacker Process) tothereby produce r-acetaldehyde.

The r-ethylene used to feed to the oxidation reactor can be a purified,partially purified, or impure r-ethylene stream. The r-ethylene can be apurified feedstock and can contain more than 98 wt. %, or at least 98.2wt. %, or at least 98.5 wt. %, or at least 98.7 wt. %, or at least 98.9wt. %, or at least 99.0 wt. %, or at least 99.2 wt. %, or at least 99.5wt. %, or at least 99.7 wt. % ethylene, based on the weight ofr-ethylene feed.

In one embodiment or in combination with any of the mentionedembodiments, a method of making a recycle content acetaldehyde productincludes an oxidation method in which a r-ethylene is fed to a reactionvessel and reacted to produce an oxidation effluent that includesr-acetaldehyde.

Although any process for converting r-ethylene to acetaldehyde can beemployed, the Wacker process is a desirable synthetic route in view ofits high catalyst activity and selectivity.

More specifically, the oxidation process for making r-acetaldehydeincludes contacting ethylene with water, a co-solvent (e.g., DMF), anoxygen-containing stream, and a catalyst complex in a reaction zone atan elevated temperature for a sufficient period of time to permitreaction of ethylene with air (particularly oxygen) to formacetaldehyde. The oxidation reaction temperature can be any temperaturefrom 50° C. to 250° C. and the reaction pressure can be from 50 kPA toabout 500 kPA. The oxidation process may or may not utilize aco-oxidant.

Suitable oxidation catalysts include any known to be effective tocatalyze the conversion of ethylene to acetaldehyde. Examples of suchcatalysts are copper salts (e.g., copper chloride), palladium salts(e.g., palladium chloride), or combinations thereof.

Conversion of the ethylene molecules in the r-ethylene can be at least80%, or at least 85%, or at least 90%, or at least 95%, or at least 97%,or at least 98%, or at least 99%. The yield will be the same values,given that no isomers of acetaldehyde exist.

The acetaldehyde may be purified by extractive distillation followed byfractional distillation.

Exemplary oxidation reactions and reactors that may be used to convertr-ethylene into acetaldehyde are described in U.S. Pat. No. 5,557,014and U.S. Patent Application Publication No. 2009/0005605, thedisclosures of which are incorporated herein by reference in theirentirety.

As shown in FIGS. 9 and 10 , the resulting r-isobutyraldehyde andr-acetaldehyde may be subjected to a hydrogenation step in order toproduce r-isobutanol and r-ethanol, respectively.

In one embodiment or in combination with any of the mentionedembodiments, a method of making a recycle content alcohol productincludes a hydrogenation step in which r-isobutyraldehyde and/orr-acetaldehyde are fed to a reaction vessel and hydrogenated to producea hydrogenation effluent that includes r-isobutanol and/or r-ethanol.

Any conventional hydrogenation process for converting r-isobutyraldehydeand r-acetaldehyde into alcohols can be employed.

Generally, the hydrogenation process for making r-isobutanol and/orr-ethanol includes contacting r-isobutyraldehyde and/or r-acetaldehydewith hydrogen and a hydrogenation catalyst in a liquid phase at anelevated temperature for a sufficient period of time. The hydrogenationreaction temperature can be any temperature from 125° C. to 300° C. andthe reaction pressure can be from 50 kPA to about 2,300 kPA.

Exemplary hydrogenation catalysts may comprise copper, iron, cobalt,nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum,titanium, zinc, chromium, rhenium, molybdenum, tungsten, or combinationsthereof. Such catalysts can include, for example, a copper-chromiumoxide catalyst. Exemplary hydrogenation catalysts are described in U.S.Pat. No. 8,426,652, the disclosure of which is incorporated herein byreference in its entirety.

The hydrogenation reaction may also utilize one more co-reactants, suchas acetic acid.

The r-ethanol and/or r-butanol may be purified by any distillationmethod known or practiced in the art.

Exemplary hydrogenation processes and reactors that may be used aredescribed in U.S. Pat. Nos. 3,340,312 and 8,426,652, the disclosures ofwhich are incorporated herein by reference in their entireties.

As shown in FIG. 10 , an alternative pathway may be utilized in order toconvert at least portion of the r-ethylene into r-ethanol. In thisalternative pathway, at least a portion of the r-ethylene may besubjected to a hydration reaction to produce r-ethanol.

In one embodiment or in combination with any of the mentionedembodiments, a method of making a recycle content ethanol productincludes a hydration step in which r-ethylene is fed to a reactionvessel and hydrated to produce a hydration effluent that includesr-ethanol.

Any conventional hydration reaction known in the art may be used toconvert r-ethylene into r-ethanol. Generally, the hydration reactioninvolves contacting the r-ethylene with steam in the presence of ahydration catalyst. The reaction is reversible, and the formation of theethanol is exothermic. Typically, only 5% of the ethylene is convertedinto ethanol at each pass through the reactor. By removing the ethanolfrom the equilibrium mixture and recycling the ethylene, it is possibleto achieve an overall 95% conversion.

The hydration reaction temperature can be any temperature from 125° C.to 350° C. and the reaction pressure can be from 20 atm to about 100atm.

The hydration catalyst may comprise an acid catalyst, such as aphosphoric acid catalyst.

The r-ethanol may be purified by any distillation method known orpracticed in the art.

Exemplary hydration methods and reactors that may be used are describedin U.S. Pat. Nos. 3,686,334 and 8,354,563, the disclosures of which areincorporated herein by reference in their entireties.

Turning again to FIGS. 9 and 10 , the resulting r-isobutanol and/orr-ethanol may be subjected to an esterification process to produce ar-mixed ester. Typically, the r-mixed esters produced from ther-isobutanol and/or r-ethanol can comprise r-isobutyl isobutyrate,r-isobutyl acetate, r-ethyl acetate, r-ethyl isobutyrate, orcombinations thereof.

One of the methods for producing the mixed esters from r-isobutanoland/or r-ethanol may involve a Fischer esterification reaction, in whicha stoichiometric excess of r-isobutanol and/or r-ethanol and an acid,such as a carboxylic acid, are heated in the presence of a catalyticamount of a strong acid (e.g., concentrated sulfuric acid or phosphoricacid) and an entrainer solvent (e.g., heptane or toluene) to yield thedesired ester. The water byproduct may be removed by azeotropicdistillation.

Generally, the acid used to produce the mixed esters may comprise acarboxylic acid. Exemplary carboxylic acids may include acetic acid,propionic acid, n-butyric acid, isobutyric acid, 2-methyl butyric acid,n-valeric acid, n-caproic acid, 2-ethyl hexanoic acid, benzoic acid, orcombinations thereof.

In one embodiment or in combination with any of the mentionedembodiments, the carboxylic acid comprises acetic acid or isobutyricacid.

The mixed ester production process may occur at a temperature in therange of 25° C. to 300° C., generally from 100° to 280° C. The reactionpressure may range from 1 to 50 bar.

Exemplary mixed esters that may be produced in accordance with themethods described herein can comprise isobutyl isobutyrate, isobutylacetate, ethyl acetate, and/or ethyl isobutyrate, or combinationsthereof.

Exemplary processes for producing mixed esters are described in U.S.Pat. Nos. 6,458,992, 6,693,213, and 7,329,774, the disclosures of whichare incorporated herein by reference in their entireties.

The r-mixed esters disclosed herein may be utilized in a vast array ofapplications, such as in coatings, solvents, adhesives, coalescents,diliuents, cleaners, coffee decaffeinators, lacquers, paint activators,paint hardeners, pesticides, insecticides, flavoring extracts, and/orplasticizers.

Producing Recycle Content Mixed Esters

In one embodiment or in combination with any of the mentionedembodiments, there is now provided a method for processing pr-ROH byfeeding the pr-ROH to a reactor in which is made mixed esters or an ECcomposition. In another embodiment, there is provided a method formaking a r-EC or pr-EC by reacting pr-ROH with an acid composition toproduce an EC effluent, optionally containing a pr-EC composition. Thereis also provided a r-EC or pr-EC, having a monomer derived from a pr-ROHcomposition. Further, there is provided a pr-EC, and other compounds orpolymers or articles made thereby.

As noted above, EC compositions can be prepared by reacting, in thepresence of an acid catalyst, pr-ROH with an acid. Optionally, at leasta portion of the pr-ROH is derived directly or indirectly from thecracking of r-pyoil to thereby obtain an r-AD composition.

In one embodiment or in combination with any of the mentionedembodiments, the concentration of pr-ROH, introduced into a reactorvessel is at least 90 wt. %, or at least 95 wt. %, or at least 97 wt. %,or at least 99 wt. %, based on the weight of the alcohol composition fedto the esterification reactor.

In one embodiment or in combination with any of the mentionedembodiments, the AD and/or ROH fed to the reaction vessels do notcontain recycle content. In another embodiment, at least a portion ofthe AD and/or ROH compositions fed to the reaction vessels are deriveddirectly or indirectly from the cracking of r-pyoil or obtained fromr-pygas. For example, at least 0.005 wt. %, or at least 0.01 wt. %, orat least 0.05 wt. %, or at least 0.1 wt. %, or at least 0.15 wt. %, orat least 0.2 wt. %, or at least 0.25 wt. %, or at least 0.3 wt. %, or atleast 0.35 wt. %, or at least 0.4 wt. %, or at least 0.45 wt. %, or atleast 0.5 wt. %, or at least 0.6 wt. %, or at least 0.7 wt. %, or atleast 0.8 wt. %, or at least 0.9 wt. %, or at least 1 wt. %, or at least2 wt. %, or at least 3 wt. %, or at least 4 wt. %, or at least 5 wt. %,or at least 6 wt. %, or at least 7 wt. %, or at least 8 wt. %, or atleast 9 wt. %, or at least 10 wt. %, or at least 11 wt. %, or at least13 wt. %, or at least 15 wt. %, or at least 20 wt. %, or at least 25 wt.%, or at least 30 wt. %, or at least 35 wt. %, or at least 40 wt. %, orat least 45 wt. %, or at least 50 wt. %, or at least 55 wt. %, or atleast 60 wt. %, or at least 70 wt. %, or at least 80 wt. %, or at least90 wt. %, or at least 95 wt. %, or at least 98 wt. %, or at least 99 wt.%, or 100 wt. % of the AD and/or ROH compositions are r-AD, pr-AD,r-ROH, or pr-ROH. In addition, or in the alternative, up to 100 wt. %,or up to 98 wt. %, or up to 95 wt. %, or up to 90 wt. %, or up to 80 wt.%, or up to 75 wt. %, or up to 70 wt. %, or up to 60 wt. %, or up to 50wt. %, or up to 40 wt. %, or up to 30 wt. %, or up to 20 wt. %, or up to10 wt. %, or up to 8 wt. %, or up to 5 wt. %, or up to 4 wt. %, or up to3 wt. %, or up to 2 wt. %, or up to 1 wt. %, or up to 0.8 wt. %, or upto 0.7 wt. %, or up to 0.6 wt. %, or up to 0.5 wt. %, or up to 0.4 wt.%, or up to 0.3 wt. %, or up to 0.2 wt. %, or up to 0.1 wt. %, or up to0.09 wt. %, or up to 0.07 wt. %, or up to 0.05 wt. %, or up to 0.03 wt.%, or up to 0.02 wt. %, or up to 0.01 wt. % of the aldehyde compositionis pr-AD, based on the weight the aldehyde composition fed to thereaction vessel and/or of the alcohol composition is pr-ROH, based onthe weight the alcohol composition fed to the reaction vessel. In eachcase, the stated amounts are also applicable to not only aldehyde and/oralcohol as fed into the reactors, but alternatively or in addition, tothe pr-AD stock and/or pr-ROH stock supplied to a manufacturer of EC, orcan be used as a basis for associating or calculating the amount ofrecycle content in pr-AD and/or pr-ROH, such as when blending a sourceof pr-AD with non-recycle content AD to make an aldehyde compositionhaving pr-AD in quantities mentioned above.

In one embodiment or in combination with any of the mentionedembodiments, the EC composition has associated with it, or contains, oris labelled, advertised, or certified as containing recycle content inan amount of at least 0.01 wt. %, or at least 0.05 wt. %, or at least0.1 wt. %, or at least 0.5 wt. %, or at least 0.75 wt. %, or at least 1wt. %, or at least 1.25 wt. %, or at least 1.5 wt. %, or at least 1.75wt. %, or at least 2 wt. %, or at least 2.25 wt. %, or at least 2.5 wt.%, or at least 2.75 wt. %, or at least 3 wt. %, or at least 3.5 wt. %,or at least 4 wt. %, or at least 4.5 wt. %, or at least 5 wt. %, or atleast 6 wt. %, or at least 7 wt. %, or at least 10 wt. %, or at least 15wt. %, or at least 20 wt. %, or at least 25 wt. %, or at least 30 wt. %,or at least 35 wt. %, or at least 40 wt. %, or at least 45 wt. %, or atleast 50 wt. %, or at least 55 wt. %, or at least 60 wt. %, or at least65 wt. % and/or the amount can be up to 100 wt. %, or up to 95 wt. %, orup to 90 wt. %, or up to 80 wt. %, or up to 70 wt. %, or up to 60 wt. %,or up to 50 wt. %, or up to 40 wt. %, or up to 30 wt. %, or up to 25 wt.%, or up to 22 wt. %, or up to 20 wt. %, or up to 18 wt. %, or up to 16wt. %, or up to 15 wt. %, or up to 14 wt. %, or up to 13 wt. %, or up to11 wt. %, or up to 10 wt. %, or up to 8 wt. %, or up to 6 wt. %, or upto 5 wt. %, or up to 4 wt. %, or up to 3 wt. %, or up to 2 wt. %, or upto 1 wt. %, or up to 0.9 wt. %, or up to 0.8 wt. %, or up to 0.7 wt. %,based on the weight of the EC composition. The recycle contentassociated with the EC can be established by applying a recycle contentvalue to the EC, such as through deducting the recycle content valuefrom a recycle inventory populated with allotments (credit orallocation) or by reacting a r-ROH feedstock to make r-EC. The allotmentcan be contained in a recycle inventory created, maintained or operatedby or for the EC manufacturer. The allotments are obtained from anysource along any manufacturing chain of products. In one embodiment, theorigin of the allotment is derived indirectly from pyrolyzing recycledwaste, or from cracking r-pyoil or from r-pygas.

The amount of recycle content in an r-ROH raw material fed to an ECreactor, or the amount of recycle content applied to the r-EC, or theamount of r-ROH needed to feed the reactor to claim a desired amount ofrecycle content in the EC in the event that all the recycle content fromthe r-ROH is applied to the EC, can be determined or calculated by anyof the following methods:

-   -   (i) the amount of an allotment associated with the r-RPJ used to        feed the reactor applied determined by the amount certified or        declared by the supplier of the alcohol composition transferred        to the manufacturer of the EC, or    -   (ii) the amount of allocation declared by the EC manufacturer as        fed to the EC reactor, or    -   (iii) using a mass balance approach to back-calculate the        minimum amount of recycle content in the feedstock from an        amount of recycle content declared, advertised, or accounted for        by the manufacturer, whether or not accurate, as applied to the        EC product, or    -   (iv) blending of non-recycle content with recycle content        feedstock EO or associating recycle content to a portion of the        feedstock, using pro-rata mass approach

Satisfying any one of the methods (i)-(iv) is sufficient to establishthe portion of r-ROH that is derived directly or indirectly fromrecycled waste, the pyrolysis of recycled waste, pyrolysis gas producedfrom the pyrolysis of recycled waste, and/or the cracking of r-pyoilproduced from the pyrolysis of recycled waste. In the event that a r-ROHfeed is blended with a recycle feed from other recycle sources, apro-rata approach to the mass of r-ROH directly or indirectly obtainedfrom recycled waste, the pyrolysis of recycled waste, pyrolysis gasproduced from the pyrolysis of recycled waste, and/or the cracking ofr-pyoil produced from the pyrolysis of recycled waste to the mass ofrecycle alcohols from other sources is adopted to determine thepercentage in the declaration attributable to r-ROH obtained directly orindirectly from recycled waste, the pyrolysis of recycled waste,pyrolysis gas produced from the pyrolysis of recycled waste, and/or thecracking of r-pyoil produced from the pyrolysis of recycled waste.

Methods (i)-(ii) need no calculation since they are determined based onwhat the ROH manufacturer or EC manufacturer or suppliers declare,claim, or otherwise communicate to each other or the public. Method(iii) and (iv) is calculated.

In one embodiment or in combination with any of the mentionedembodiments, the minimum amount of recycle content ROH fed to thereactor can be determined by knowing the amount of recycle contentassociated with the end product EC and assuming that the entire recyclecontent in the EC is attributable to the r-ROH fed to the reactor andnone to the acid fed to the reactor. The minimum portion of r-ROHcontent derived directly or indirectly from recycled waste, thepyrolysis of recycled waste, pyrolysis gas produced from the pyrolysisof recycled waste, and/or the cracking of r-pyoil produced from thepyrolysis of recycled waste, to make an EC product associated with aparticular amount of recycle content, can be calculated as:

$P = {\left( \frac{\% D}{100} \right) \times \left( \frac{Pm}{Rm} \right) \times \left( \frac{100}{Y} \right) \times 100}$

where P means the minimum portion of r-ROH derived directly orindirectly recycled waste, the pyrolysis of recycled waste, pyrolysisgas produced from the pyrolysis of recycled waste, and/or the crackingof r-pyoil produced from the pyrolysis of recycled waste, and

% D means the percentage of recycle content declared in product r-EC,and

Pm means the molecular weight of product EC, and

Rm means the molecular weight of reactant ROH as a moiety in EC product,not to exceed the molecular weight of the reactant ROH, and

Y means the percent yield of the product, e.g. EC, determined as anaverage annual yield regardless of whether or not the feedstock isr-ROH. If an average annual yield is not known, the yield can be assumedto be industry average using the same process technology.

The amount of recycle content in the r-ROH feed can be greater than thedesignation of recycle content in the EC. For instance, the amount ofrecycle content in the r-ROH feed could be 12%, thereby resulting inexcess recycle content left over if the designation of recycle contentin the EC is at only 10%. In another example, the r-ROH may contain 50%recycle content, and only 10% is ascribed to the EC, with the remainderavailable to the product reserved in a recycle inventory. The excessrecycle content may be stored in a recycle inventory and applied toother EC products that either are not made with r-ROH or with adeficient amount of r-ROH recycle content relative to the amount ofrecycle content one desires to apply to the EC. However, whether or notthe r-ROH feedstock actually was designated by the manufacturer of theEC as containing the minimum amount of recycle content, a r-ECdesignated as containing a certain recycle content is neverthelessdeemed to have been made from a r-ROH feedstock containing the minimumrecycle content by the calculation method described above.

In the case of a pro-rata mass approach in method (iv), the portion ofr-ROH derived directly or indirectly from recycled waste, the pyrolysisof recycled waste, pyrolysis gas produced from the pyrolysis of recycledwaste, and/or the cracking of r-pyoil produced from the pyrolysis ofrecycled waste would be calculated on the basis of the mass of recyclecontent available to the EC manufacturer by way of purchase or transferor created in case the ROH is integrated into r-ROH production, that isattributed to the feedstock on a daily run divided by the mass of ther-ROH feedstock, or:

$P = {\frac{Mr}{Ma} \times 100}$

-   -   where P means the percentage of recycle content in the ROH        feedstock stream, and    -   where Mr is the mass of recycle content attributed to the r-ROH        stream on a daily basis, and    -   Ma is the mass of the entire ROH feedstock used to make EC on        the corresponding day.

For example, if an EC manufacturer has available 1000 kg of a recycleallocation or credit that has its origin in pyrolyzing recycled waste,and the EC manufacturer elects to attribute 10 kg of the recycleallocation to an ROH feedstock used to make the EC, and the ROHfeedstock employs 100 kg per day to make EC, the portion P of r-ROHfeedstock derived directly or indirectly from cracking pyoil would be 10kg/100 kg, or 10 wt %. The ROH feedstock composition would be consideredto be a r-ROH composition because a portion of the recycle allocation isapplied to the ROH feedstock used to make the EC.

In another embodiment, there is provided a variety of methods forapportioning the recycle content among the various products made by anEC manufacturer or the products made by any one entity or a combinationsof entities among the Family of Entities of which the EC manufacturer isa part. For example, the EC manufacturer, of any combination or theentirety of its Family of Entities, or a Site, can:

-   -   a. adopt a symmetric distribution of recycle content values        among its product(s) based on the same fractional percentage of        recycle content in one or more feedstocks, or based on the        amount of allotment received. For example, if 5 wt. % of the ROH        feedstock is r-ROH, or if the allotment value is 5 wt. % of the        entire ROH feedstock, then all EC made with the ROH feedstock        may contain 5 wt. % recycle content value. In this case, the        amount of recycle content in the products is proportional to the        amount of recycle content in the feedstock to make the products;        or    -   b. adopt an asymmetric distribution of recycle content values        among its product(s) based on the same fractional percentage of        recycle content in the one or more feedstocks, or based on the        amount of allotment received. For example, if 5 wt. % of the ROH        feedstock is r-ROH, or if the allotment value is 5 wt. % of the        entire ROH feedstock, then one volume or batch of EC can receive        a greater amount of recycle content value that other batches or        volume of EC made, provided that the total amount of recycle        content does not exceed the total amount of r-ROH or allotment        received, or the total amount of recycle content in the recycle        inventory. One batch of EC can contain 5% recycle content by        mass, and another batch can contain zero 0% recycle content,        even though both volumes are made from the same volume of ROH        feedstock. In the asymmetric distribution of recycle content, a        manufacturer can tailor the recycle content to volumes of EC        sold as needed among customers, thereby providing flexibility        among customers some of whom may need more recycle content than        others in an EC volume.

Both the symmetric distribution and the asymmetric distribution ofrecycle content can be proportional on a site wide basis, or on amulti-site basis. In one embodiment or in combination with any of thementioned embodiments, the recycle content input (recycle contentfeedstock or allotments) can be to a Site, and recycle content valuesfrom said inputs are applied to one or more products made at the sameSite, and at least one of the products made at the Site is EC, andoptionally at least a portion of the recycle content value is applied tothe EC products. The recycle content values can be applied symmetricallyor asymmetrically to the products at the Site. The recycle contentvalues can be applied across different EC volumes symmetrically orasymmetrically, or applied across a combination of EC and other productsmade at the Site. For example, a recycle content value is transferred toa recycle inventory at a Site, created at a Site, or a feedstockcontaining recycle content value is reacted at a Site (collectively the“a recycle input”), and recycle content values obtained from said inputsare:

-   -   a. distributed symmetrically across at least a portion or across        all EC volume made at the Site over a period of time (e.g.        within 1 week, or within 1 month, or within 6 months, or within        the same calendar year, or continuously); or    -   b. distributed symmetrically across at least a portion or across        all EC volume made at the Site and across at least a portion or        across a second different product made at the same Site, each        over the same period of time (e.g. within 1 week, or within 1        month, or within 6 months, or within the same calendar year, or        continuously); or    -   c. recycle content is distributed symmetrically across all        products to which recycle content is actually applied that are        made at the Site, over the same period of time (e.g. within the        same day, or within 1 week, or within 1 month, or within 6        months, or within the same calendar year, or continuously).        While a variety of products can be made at a Site, in this        option, not all product have to receive a recycle content value,        but for all products that do receive or to which are applied a        recycle content value, the distribution is symmetrical; or    -   d. distributed asymmetrically across at least two EC volumes        made at the same Site, optionally either over the same period of        time (e.g. within 1 day, or within 1 week, or within 1 month, or        within 6 months, or within a calendar year, or continuously), or        as sold to at least two different customers. For example, one        volume of EC made can have a greater recycle content value than        a second volume of EC made at the Site, or one volume of EC made        at the Site and sold to one customer can have a greater recycle        content value than a second volume of EC made at the Site and        sold to a second different customer, or    -   e. distributed asymmetrically across at least one volume of EC        and at least one volume of a different product, each made at the        same Site, optionally either over the same period of time (e.g.        within 1 day, or within 1 week, or within 1 month, or within 6        months, or within a calendar year, or continuously), or as sold        to at least two different customers.

In one embodiment or in combination with any of the mentionedembodiments, the recycle content input or creation (recycle contentfeedstock or allotments) can be to or at a first Site, and recyclecontent values from said inputs are transferred to a second Site andapplied to one or more products made at a second Site, and at least oneof the products made at the second Site is EC, and optionally at least aportion of the recycle content value is applied to EC products made atthe second Site. The recycle content values can be applied symmetricallyor asymmetrically to the products at the second Site. The recyclecontent values can be applied across different EC volumes symmetricallyor asymmetrically, or applied across a combination of EC and otherproducts made at the second Site. For example, a recycle content valueis transferred to a recycle inventory at a first Site, created at afirst Site, or a feedstock containing recycle content value is reactedat a first Site (collectively the “a recycle input”), and recyclecontent values obtained from said inputs are:

-   -   a. distributed symmetrically across at least a portion or across        all EC volume made at a second Site over a period of time (e.g.        within 1 week, or within 1 month, or within 6 months, or within        the same calendar year, or continuously); or    -   b. distributed symmetrically across at least a portion or across        all EC volume made at the second Site and across at least a        portion or across a second different product made at the same        second Site, each over the same period of time (e.g. within 1        week, or within 1 month, or within 6 months, or within the same        calendar year, or continuously); or    -   c. recycle content is distributed symmetrically across all        products to which recycle content is actually applied that are        made at the second Site, over the same period of time (e.g.        within the same day, or within 1 week, or within 1 month, or        within 6 months, or within the same calendar year, or        continuously). While a variety of products can be made at a        second Site, in this option, not all product have to receive a        recycle content value, but for all products that do receive or        to which are applied a recycle content value, the distribution        is symmetrical; or    -   d. distributed asymmetrically across at least two EC volumes        made at the same second Site, optionally either over the same        period of time (e.g. within 1 day, or within 1 week, or within 1        month, or within 6 months, or within a calendar year, or        continuously), or as sold to at least two different customers.        For example, one volume of EC made can have a greater recycle        content value than a second volume of EC each made at the second        Site, or one volume of EC made at the second Site and sold to        one customer can have a greater recycle content value than a        second volume of EC made at the second Site and sold to a second        different customer, or    -   e. distributed asymmetrically across at least one volume of EC        and at least one volume of a different product, each made at the        same second Site, optionally either over the same period of time        (e.g. within 1 day, or within 1 week, or within 1 month, or        within 6 months, or within a calendar year, or continuously), or        as sold to at least two different customers.

In one embodiment or in combination with any of the mentionedembodiments, the EC manufacturer, or one among its Family of Entities,can make EC, or process an ROH, or process ROH and make an r-EC, or maker-EC, by obtaining any source of an alcohol composition from a supplier,whether or not such aldehyde composition has any direct or indirectrecycle content, and either:

-   -   i. from the same supplier of the alcohol composition, also        obtain a recycle content allotment, or    -   ii. from any person or entity, obtaining a recycle content        allotment without a supply of an alcohol composition from the        person or entity transferring the recycle content allotment.

The allotment in (i) is obtained from an ROH supplier, and the ROHsupplier also supplies ROH to the EC manufacturer or within its Familyof Entities. The circumstance described in (i) allows an EC manufacturerto obtain a supply of an aldehyde composition that is a non-recyclecontent ROH, yet obtain a recycle content allotment from the ROHsupplier. In one embodiment or in combination with any of the mentionedembodiments, the ROH supplier transfers a recycle content allotment tothe EC manufacturer and a supply of ROH to the EC manufacturer, wherethe recycle content allotment is not associated with the ROH supplied,or even not associated with any ROH made by the ROH supplier. Therecycle content allotment does not have to be tied to an amount ofrecycle content in an aldehyde composition or to any monomer used tomake EC, but rather the recycle content allotment transferred by the ROHsupplier can be associated with other products derived directly orindirectly from recycled waste, the pyrolysis of recycled waste,pyrolysis gas produced from the pyrolysis of recycled waste, and/or thecracking of r-pyoil produced from the pyrolysis of recycled waste or therecycle content of any downstream compounds obtained from the pyrolysisof recycled waste, such as r-ethylene, r-propylene, r-butadiene,r-aldehydes, r-alcohols, r-benzene, r-AD, etc. For example, the ROHsupplier can transfer to the EC manufacturer a recycle contentassociated with r-propylene, r-ethylene, and/or r-AD also supply aquantity of ROH even though r-propylene, r-ethylene, and/or r-AD werenot used in the synthesis of the ROH. This allows flexibility among theROH supplier and EC manufacturer to apportion a recycle content amongthe variety of products they each make.

In one embodiment or in combination with any of the mentionedembodiments, the ROH supplier transfers a recycle content allotment tothe EC manufacturer and a supply of ROH to the EC manufacturer, wherethe recycle content allotment is associated with ROH. In this case, theROH transferred does not have to be a r-ROH (one that is deriveddirectly or indirectly from the pyrolysis of recycled waste); rather theROH supplied by the supplier can be any ROH such as a non-recyclecontent ROH, so long as the allocation supplied is associated with amanufacture of ROH. Optionally, the ROH being supplied can be r-ROH andat least a portion of the recycle content allotment being transferredcan be the recycle content in the r-ROH. The recycle content allotmenttransferred to the EC manufacturer can be up front with the ROH suppliedin installments, or with each ROH installment, or apportioned as desiredamong the parties.

The allotment in (ii) is obtained by the EC manufacturer (or its Familyof Entities) from any person or entity without obtaining a supply of ROHfrom the person or entity. The person or entity can be an ROHmanufacturer that does not supply ROH to the EC manufacturer or itsFamily of Entities, or the person or entity can be a manufacturer thatdoes not make ROH. In either case, the circumstances of (ii) allows anEC manufacturer to obtain a recycle content allotment without having topurchase any ROH from the entity supplying the recycle contentallotment. For example, the person or entity may transfer a recyclecontent allotment through a buy/sell model or contract to the ECmanufacturer or its Family of Entities without requiring purchase orsale of an allotment (e.g. as a product swap of products that are notROH), or the person or entity may outright sell the allotment to the ECmanufacturer or one among its Family of Entities. Alternatively, theperson or entity may transfer a product, other than ROH, along with itsassociated recycle content allotment to the EC manufacturer. This can beattractive to an EC manufacturer that has a diversified business makinga variety of products other than EC requiring raw materials other thanROH that the person or entity can supply to the EC manufacturer.

The EC manufacturer can deposit the allotment into a recycle inventory.The EC manufacturer also makes EC, whether or not a recycle content isapplied to the EC so made and whether or not a recycle content value, ifapplied to the EC, is drawn from the recycle inventory. For example, theEC manufacturer, or any entity among its Family of Entities may:

-   -   a. deposit the allotment into a recycle inventory and merely        store it; or    -   b. deposit the allotment into a recycle inventory and apply a        recycle content value from the recycle inventory to products        other than EC made by the EC manufacturer, or    -   c. sell or transfer an allotment from the recycle inventory into        which the allotment obtained as noted above was deposited.

If desired, however, from that recycle inventory, any allotment can bededucted and applied to the EC product in any amount and at any time upto the point of sale or transfer of the EC to a third party. Thus, therecycle content allotment applied to the EC can be derived directly orindirectly from pyrolyzing recycled waste, or the recycle contentallotment applied to the EC is not derived directly or indirectly fromthe pyrolysis of recycled waste. For example, a recycle inventory ofallotments can be generated having a variety of sources for creating theallotments. Some recycle content allotments (credits) can have theirorigin in methanolysis of recycled waste, or from gasification ofrecycled waste, or from mechanical recycling of waste plastic or metalrecycling, and/or from pyrolyzing recycled waste, or from any otherchemical or mechanical recycling technology. The recycle inventory mayor may not track the origin or basis of obtaining a recycle content, orthe recycle inventory may not allow one to associate the origin or basisof an allocation to the allocation applied to EC. Thus, in thisembodiment, it is sufficient that a recycle content value is deductedfrom recycle inventory and applied to EC regardless of the source ororigin of the recycle content value, provided that an allotment derivedfrom pyrolyzing recycled waste is also obtained by the EC manufactureras specified in step (i) or step (ii), whether or not that allotment isactually deposited into the recycle inventory. In one embodiment or incombination with any of the mentioned embodiments, the allotmentobtained in step (i) or (ii) is deposited into a recycle inventory ofallotments. In one embodiment or in combination with any of thementioned embodiments, the recycle content value deducted from therecycle inventory and applied to the EC originates from pyrolyzingrecycled waste.

As used throughout, the recycle inventory of allotments can be owned bythe EC manufacturer, operated by the EC manufacturer, owned or operatedby other than the EC manufacturer but at least in part for the ECmanufacturer, or licensed by the EC manufacturer. Also, as usedthroughout, the EC manufacturer may also include its Family of Entities.For example, while the EC manufacturer may not own or operate therecycle inventory, one among its Family of Entities may own such aplatform, or license it from an independent vendor, or operate it forthe EC manufacturer. Alternatively, an independent entity may own and/oroperate the recycle inventory and for a service fee operate and/ormanage at least a portion of the recycle inventory for the ECmanufacturer.

In one embodiment or in combination with any of the mentionedembodiments, the EC manufacturer obtains a supply of ROH from asupplier, and also obtains an allotment from either (i) the supplier or(ii) from any other person or entity, where such allotment is derivedfrom recycled waste, the pyrolysis of recycled waste, pyrolysis gasproduced from the pyrolysis of recycled waste, and/or the cracking ofr-pyoil produced from the pyrolysis of recycled waste, and optionallythe allotment is obtained from the ROH supplier and can even be anallotment by virtue of obtaining a r-ROH from the supplier. The ECmanufacturer is deemed to obtain the supply of ROH from a supplier ifthe supply is obtained by a person or entity within the Family ofEntities of the EC manufacturer. The EC manufacturer then carries outone or more of the following steps:

-   -   a. applying the allotment to EC made by the supply of ROH;    -   b. applying the allotment to EC not made by the supply of ROH,        such as would be the case where EC is already made and stored in        recycle inventory, or to future made EC; or    -   c. depositing the allotment into a recycle inventory from which        is deducted a recycle content value and applying at least a        portion of the recycle content value to:        -   i. EC to thereby obtain r-EC, or        -   ii. to a compound or composition other than EC, or        -   iii. both;    -   whether or not r-ROH is used to make the EC composition, and        whether or not the recycle content value applied to EC was        obtained from a recycle content value in the allotment obtained        in step (i) or step (ii) or deposited into the recycle        inventory; or    -   d. as described above, can merely be deposited into a recycle        inventory and stored.

It is not necessary in all embodiments that r-ROH is used to make ther-EC composition or that the r-EC was obtained from a recycle contentallotment associated with an alcohol composition. Further, it is notnecessary that an allotment be applied to the feedstock for making theEC to which recycle content is applied. Rather, as noted above, theallotment, even if associated with an aldehyde composition when thealdehyde composition is obtained from a supplier, can be deposited intoan electronic recycle inventory. In one embodiment or in combinationwith any of the mentioned embodiments, however, r-ROH is used to makethe r-EC composition. In one embodiment or in combination with any ofthe mentioned embodiments, the r-EC is obtained from a recycle contentallotment associated with an alcohol composition. In one embodiment orin combination with any of the mentioned embodiments, at least a portionof r-ROH allotments are applied to EC to make a r-EC.

The mixed ester composition can be made from any source of an alcoholcomposition, whether or not the alcohol composition is a r-ROH, andwhether or not the ROH is obtained from a supplier or made by the ECmanufacturer or within its Family of Entities. Once an EC composition ismade, it can be designated as having recycle content based on andderived from at least a portion of the allotment, again whether or notthe r-ROH is used to make the r-EC composition and regardless of thesource of ROH used to make the EC. The allocation can be withdrawn ordeducted from recycle inventory. The amount of the deduction and/orapplied to the EC can correspond to any of the methods described above,e.g., a mass balance approach.

In one embodiment or in combination with any of the mentionedembodiments, a recycle content mixed ester composition can be made byreacting an alcohol composition obtained from any source in a syntheticprocess to make an EC, and a recycle content value can be applied to atleast a portion of the EC to thereby obtain r-EC. Optionally, a recyclecontent value can be obtained by deducting from a recycle inventory. Theentire amount of recycle content value in the EC can correspond to therecycle content value deducted from the recycle inventory. Recyclecontent value deducted from the recycle inventory can be applied to bothEC and products or compositions other than EC made by the ECmanufacturer or a person or entity among its Family of Entities. Thealcohol composition can be obtained from a third party, or made by theEC manufacturer, or made by a person or entity amount the Family ofEntities of the EC manufacturer and transferred to the EC manufacturer.In another example, the EC manufacturer or its Family of Entities canhave a first facility for making alcohol within a first Site, and asecond facility within the first Site or a second facility within asecond Site where the second facility makes EC, and transfer the alcoholfrom the first facility or first Site to the second facility or secondSite. The facilities or Sites can be in direct or indirect, continuousor discontinuous, fluid communication or pipe communication with eachother. A recycle content value is then applied to (e.g. assigned to,designate to correspond to, attributed to, or associated with) the EC tomake a r-EC. At least a portion of the recycle content value applied tothe EC is obtained from a recycle inventory.

Optionally, one may communicate to a third party that the r-EC hasrecycle content or is obtained or derived from recycled waste. In oneembodiment or in combination with any of the mentioned embodiments, onemay communicate recycle content information about the EC to a thirdparty where such recycle content information is based on or derived fromat least a portion of the allocation or credit. The third party may be acustomer of the EC manufacturer or supplier, or may be any other personor entity or governmental organization other than the entity owning theEC. The communication may electronic, by document, by advertisement, orany other means of communication.

In one embodiment or in combination with any of the mentionedembodiments, a recycle content mixed ester composition is obtained byeither making a first r-EC or by merely possessing (e.g. by way ofpurchase, transfer, or otherwise) a first r-EC already having a recyclecontent, and transferring a recycle content value between a recycleinventory and the first r-EC to obtain a second r-EC having differentrecycle content value than the first r-EC.

In one embodiment or in combination with any of the mentionedembodiments, the transferred recycle content value described above isdeducted from the recycle inventory and applied to the first r-EC toobtain a second r-EC having a second recycle content value higher thanthe first r-EC contains, to thereby increase the recycle content infirst r-EC.

The recycle content in the first r-EC need not be obtained from arecycle inventory, but rather can be attributed to EC by any of themethods described herein (e.g. by virtue of using a r-ROH as a reactantfeed), and the EC manufacturer may seek to further increase the recyclecontent in the first r-EC so made. In another example, an EC distributormay have r-EC in its inventory and seek to increase the recycle contentvalue of the first r-EC in its possession. The recycle content in thefirst r-EC can be increased by applying a recycle content valuewithdrawn from a recycle inventory.

The recycle content value quantity that is deducted from recycleinventory is flexible and will depend on the amount of recycle contentapplied to the EC. In one embodiment or in combination with any of thementioned embodiments, it is at least sufficient to correspond with atleast a portion of the recycle content in the r-EC. This is useful if,as noted above, a portion of the EC was made with r-ROH where therecycle content value in the r-ROH was not deposited into a recycleinventory, resulting in a r-EC and one desires to increase the recyclecontent in the r-EC by applying a recycle content value withdrawn from arecycle inventory; or where one possesses r-EC (by way of purchase,transfer, or otherwise) and desires to increase its recycle contentvalue. Alternatively, the entire recycle content in the r-EC can beobtained by applying a recycle content value to the EC obtained from arecycle inventory.

The method for calculating the recycle content value is not limited, andcan include the mass balance approach or the methods of calculationdescribed above. The recycle inventory can be established on any basisand be a mix of basis. Examples of the origin for obtaining allotmentsdeposited into a recycle inventory can be from pyrolyzing recycledwaste, gasification of recycled waste, depolymerization of recycledwaste such as through hydrolysis or methanolysis, and so on. In oneembodiment or in combination with any of the mentioned embodiments, atleast a portion of the allocations deposited into the recycle inventoryis attributable to pyrolyzing recycled waste (e.g. obtained fromcracking r-pyoil or obtained from r-pygas). The recycle inventory may ormay not track the origin of recycle content value deposited into therecycle inventory. In one embodiment or in combination with any of thementioned embodiments, the recycle inventory distinguishes between arecycle content value obtained from pyrolyzing recycled waste (i.e.,pyrolysis recycle content value) and recycle content values having theirorigin in other technologies (i.e., recycle content value). This may beaccomplished simply by assigning distinguishing units of measure to therecycle content values having is origin in pyrolyzing recycled waste, ortracking the origin of the allocation by assigning or placing theallocation into a unique module, unique spreadsheet, unique column orrow, unique database, unique taggants associated with a unit of measure,and the like to as to distinguish the:

-   -   a. Origin of technology used to create the allotment, or    -   b. The type of compound having recycle content from which the        allocation is obtained, or    -   c. The supplier or Site identity, or    -   d. A combination thereof.

The recycle content value applied to the EC from the recycle inventorydoes not have to be obtained from allotments having their origin inpyrolyzing recycled waste. The recycle content values deducted from therecycle inventory and/or applied to the EC can be derived from anytechnology used to generate allocations from recycled waste, such asthrough methanolysis or gasification of recycled waste. In oneembodiment or in combination with any of the mentioned embodiments,however, the recycle content value applied to the EC orwithdrawn/deducted from the recycle inventory have their origins or arederived from allotments obtained from pyrolyzing recycled waste.

The following are examples of applying (designating, assigning, ordeclaring a recycle content) a recycle content value or allotment to ECor to an aldehyde composition:

-   -   1. Applying at least a portion of a recycle content value to an        EC composition where the recycle content value is derived        directly or indirectly with a recycle content ethylene or        propylene, where such recycle content ethylene or propylene is        obtained directly or indirectly from cracking r-pyoil or        obtained from r-pygas, and the aldehyde composition used to make        the EC did not contain any recycle content or it did contain        recycle content; or    -   2. Applying at least a portion of a recycle content value to an        EC composition where the recycle content value is derived        directly or indirectly from cracking r-pyoil or obtained from        r-pygas; or    -   3. Applying at least a portion of a recycle content value to an        EC composition where the recycle content value is derived        directly or indirectly with a r-AD, whether or not such aldehyde        volume is used to make the EC; or    -   4. Applying at least a portion of a recycle content value to an        EC composition where the recycle content value is derived        directly or indirectly with a r-ROH, whether or not such alcohol        volume is used to make the EC; or    -   5. Applying at least a portion of a recycle content value to an        EC composition where the recycle content value is derived        directly or indirectly with a r-ROH, and the r-ROH is used as a        feedstock to make the r-EC to which the recycle content value is        applied, and:        -   a. all of the recycle content in the r-alcohol is applied to            determine the amount of recycle content in the EC, or        -   b. only a portion of the recycle content in the r-alcohol is            applied to determine the amount of recycle content applied            to the EC, the remainder stored in recycle inventory for use            to future EC, or for application to other existing EC made            from r-ROH not containing any recycle content, or to            increase the recycle content on an existing r-EC, or a            combination thereof, or        -   c. none of the recycle content in the r-ROH is applied to            the EC and instead is stored in a recycle inventory, and a            recycle content from any source or origin is deducted from            the recycle inventory and applied to EC; or    -   6. Applying at least a portion of a recycle content value to an        aldehyde composition used to make an EC to thereby obtain a        r-EC, where the recycle content value was obtained with the        transfer or purchase of the same aldehyde composition used to        make the EC and the recycle content value is associated with the        recycle content in an aldehyde composition; or    -   7. Applying at least a portion of a recycle content value to an        aldehyde composition used to make an EC to thereby obtain a        r-EC, where the recycle content value was obtained with the        transfer or purchase of the same aldehyde composition used to        make the EC and the recycle content value is not associated with        the recycle content in an alcohol composition but rather on the        recycle content of a monomer used to make the alcohol        composition, such as with propylene or ethylene; or    -   8. Applying at least a portion of a recycle content value to an        aldehyde composition used to make an EC to thereby obtain a        r-EC, where the recycle content value was not obtained with the        transfer or purchase of the alcohol composition and the recycle        content value is associated with the recycle content in the        alcohol composition; or    -   9. Applying at least a portion of a recycle content value to an        alcohol composition used to make an EC to thereby obtain a r-EC,        where the recycle content value was not obtained with the        transfer or purchase of the alcohol composition and the recycle        content value is not associated with the recycle content in the        alcohol composition but rather with the recycle content of any        monomers used to make the alcohol composition, such as a recycle        content value associated with recycle content in propylene or        ethylene; or    -   10. Obtaining a recycle content value derived directly or        indirectly from pyrolyzing recycled waste, such as from cracking        of r-pyoil, or obtained from a r-pygas, or associated with a        r-composition, or associated with a r-ROH, and:        -   a. no portion of the recycle content value is applied to an            alcohol composition to make EC and at least a portion is            applied to EC to make a r-EC; or        -   b. less than the entire portion is applied to an aldehyde            composition used to make EC and the remainder is stored in            recycle inventory or is applied to future made EC or is            applied to existing EC in recycle inventory.

As used throughout, the step of deducting an allocation from a recycleinventory does not require its application to an EC product. Thededuction also does not mean that the quantity of the deductiondisappears or is removed from the inventory logs. A deduction can be anadjustment of an entry, a withdrawal, an addition of an entry as adebit, or any other algorithm that adjusts inputs and outputs based onan amount of recycle content associated with a product and one or acumulative amount of allocations on deposit in the recycle inventory.For example, a deduction can be a simple step of a reducing/debit entryfrom one column and an addition/credit to another column within the sameprogram or books, or an algorithm that automates the deductions andentries/additions and/or applications or designations to a productslate. The step of applying a recycle content value to an EC productalso does not require the recycle content value or allocation to beapplied physically to an EC product or to any document issued inassociation with the EC product sold. For example, an EC manufacturermay ship EC product to a customer and satisfy the “application” of therecycle content value to the EC product by electronically transferring arecycle content credit or certification document to the customer, or byapplying a recycle content value to a package or container containingthe EC or r-ROH.

Some EC manufacturers may be integrated into making downstream productsusing EC as a raw material, such as making coatings, solvents,adhesives, coalescents, diluents, cleaners, coffee decaffeinators,lacquers, paint activators, paint hardeners, pesticides, insecticides,flavoring extracts, and/or plasticizers. They, and other non-integratedEC manufacturers, can also offer to sell or sell EC on the market ascontaining or obtained with an amount of recycle content. The recyclecontent designation can also be found on or in association with thedownstream product made with the EC.

In one embodiment or in combination with any of the mentionedembodiments, the amount of recycle content in the r-ROH or in the r-ECwill be based on the allocation or credit obtained by the manufacturerof the EC composition or the amount available in the EC manufacturer'srecycle inventory. A portion or all of the recycle content value in anallocation or credit obtained by or in the possession of a manufacturerof EC can be designated and assigned to a r-ROH or r-EC on a massbalance basis. The assigned value of the recycle content to the r-ROH orr-EC should not exceed the total amount of all allocations and/orcredits available to the manufacturer of the EC or other entityauthorized to assign a recycle content value to the EC.

There is now also provided a method of introducing or establishing arecycle content in a mixed ester without necessarily using an r-ROHfeedstock. In this method,

-   -   a. an olefin supplier either:        -   i. cracks a cracker feedstock comprising recycle pyoil to            make an olefin composition at least a portion of which is            obtained by cracking said recycle pyoil (r-olefin), or        -   ii. makes a pygas at least a portion of which is obtained by            pyrolyzing a recycled waste stream (r-pygas), or        -   iii. both; and    -   b. a mixed ester manufacturer:        -   i. obtaining an allotment derived directly or indirectly            with said r-olefin or said r-pygas from the supplier or a            third-party transferring said allotment,        -   ii. making a mixed ester from an alcohol, and        -   iii. associating at least a portion of the allotment with at            least a portion of the mixed ester, whether or not the            alcohol used to make the mixed ester contains r-ROH.

In this method, the mixed ester manufacturer need not purchase r-ROHfrom any entity or from the supplier of alcohol, and does not requirethe mixed ester manufacturer to purchase olefins, r-olefins, AD, r-AD,or ROH from a particular source or supplier, and does not require themixed ester manufacturer to use or purchase an ROH composition havingr-ROH in order to successfully establish a recycle content in the mixedester composition. The ROH manufacturer may use any source of ROH andapply at least a portion of the allocation or credit to at least aportion of the ROH feedstock or to at least a portion of the mixed esterproduct. When the allocation or credit is applied to the feedstock ROH,this would be an example of an r-ROH feedstock indirectly derived fromthe cracking of r-pyoil or obtained from r-pygas. The association by themixed ester manufacturer may come in any form, whether by on in itsrecycle inventory, internal accounting methods, or declarations orclaims made to a third party or the public.

In another embodiment, an exchanged recycle content value is deductedfrom a first r-EC and added to the recycle inventory to obtain a secondr-EC having a second recycle content value lower than the first r-ECcontains, to thereby decrease the recycle content in first r-EC. Thisembodiment, the above description concerning adding a recycle contentvalue from a recycle inventory to a first r-EC applies in reverse todeducting a recycle content from first r-EC and adding it to a recycleinventory.

The allotment can be obtained from a variety of sources in themanufacturing chain starting from pyrolyzing recycled waste up to makingand selling a r-ROH. The recycle content value applied to EC or theallocation deposited into the recycle inventory need not be associatedwith r-ROH. In one embodiment or in combination with any of thementioned embodiments, the process for making r-EC can be flexible andallow for obtaining an allocation anywhere along the manufacturing chainto make EC starting from pyrolyzing recycled waste. For example, one canmake r-EC by:

-   -   a. pyrolyzing a pyrolysis feed comprising a recycled waste        material to thereby form a pyrolysis effluent that contains        r-pyoil and/or r-pygas. An allotment associated with the r-pyoil        or r-pygas is automatically created by creation of pyoil or        pygas from a recycled waste stream. The allotment may travel        with the pyoil or pygas, or be dissociated from the pyoil or        pygas such as by way of depositing the allotment into a recycle        inventory; and    -   b. optionally cracking a cracker feed that contains at least a        portion of the r-pyoil made in step a) to thereby produce a        cracker effluent containing r-olefins; or optionally cracking a        cracker feed without r-pyoil to make olefins and applying a        recycle content value to the olefins so made by deducting a        recycle content value from a recycle inventory (in the case that        can be owned, operated, or for the benefit of an olefin producer        or its Family of Entities) and applying the recycle content        value to the olefins to make r-olefins;    -   c. reacting any olefin volume in a synthetic process to make an        AD and/or ROH composition; optionally using the olefin made in        step b) and optionally using a r-olefin made in step b) and        optionally applying a recycle content value associated the        manufacture of the aldehydes or alcohols made to make r-ROH; and    -   d. reacting any ROH in a synthetic process to make a mixed        ester; optionally using the ROH made in step c) and optionally        using a r-ROH made in step c); and    -   e. applying a recycle content value to at least a portion of        said mixed ester composition based on:        -   i. feeding r-ROH as a feedstock or        -   ii. depositing at least a portion of an allotment obtained            from any one or more of steps a) or b) or c) into a recycle            inventory and deducting from said inventory a recycle            content value and applying at least a portion of either or            both of said values to EC to thereby obtain r-EC.

In one embodiment or in combination with any of the mentionedembodiments, there is also provided a comprehensive process for makingrecycle content mixed esters by:

-   -   a. making a r-olefin by either cracking the r-pyoil or        separating an olefin from the r-pygas; and    -   b. converting at least a portion of the r-olefin in a synthetic        process to make aldehyde or alcohol, and    -   c. optionally converting at least a portion of any or said        aldehyde to an alcohol; and    -   d. converting at least a portion of any or said alcohol to a        mixed ester; and    -   e. applying a recycle content value to said mixed ester to make        a r-EC; and    -   f. optionally, also making a r-pyoil or r-pygas or both by        pyrolyzing a recycle feedstock

In this embodiment, all steps a)-f) can be practiced by and within aFamily of Entities, or optionally on the same Site.

In another method, the direct method, a recycle content can beintroduced or established in mixed ester by:

-   -   a. obtaining recycle alcohol composition at least a portion of        which is directly derived from cracking r-pyoil or obtained from        r-pygas (“r-ROH”),    -   b. making a mixed ester composition from a feedstock comprising        r-ROH,    -   c. applying a recycle content value to at least a portion of any        mixed ester composition made by the same entity that made the        mixed ester composition in step b), and the recycle content        value is based at least partly on the amount of recycle content        contained in the r-ROH.

In another more detailed direct method, a recycle content can beintroduced or established in mixed ester by:

-   -   a. making a recycle olefin composition (e.g., ethylene or        propylene) at least a portion of which is directly derived from        the pyrolysis of recycle waste or from cracking r-pyoil or        obtained from r-pygas (“dr-propylene”),    -   b. optionally making a dr-aldehyde with a feedstock containing        dr-propylene and/or dr-ethylene,    -   c. making an alcohol with a feedstock comprising the dr-ethylene        and/or aldehyde,    -   d. designating at least a portion of the alcohol as containing a        recycle content corresponding to at least a portion of the        amount of dr-propylene and/or dr-ethylene contained in the        feedstock to obtain a dr-alcohol,    -   e. making a mixed ester with a feedstock containing r-alcohol,    -   f. designating at least a portion of the mixed ester as        containing a recycle content corresponding to at least a portion        of the amount of dr-alcohol contained in the feedstock to obtain        a dr-mixed ester,    -   g. and optionally offering to sell or selling the r-mixed ester        as containing or obtained with recycle content corresponding        with such designation.

In these direct methods, the r-ROH content used to make the mixed esterwould be traceable to the olefin made by a supplier by cracking r-pyoilor obtained from r-pygas. Not all of the amount of r-olefin used to makethe alcohol need be designated or associated with the alcohol. Forexample, if 1000 kg of r-ethylene is used to make r-ROH, the alcoholmanufacturer can designate less than 1000 kg of recycle content toward aparticular batch of feedstock used to make the alcohol and may insteadspread out the 1000 kg recycle content amount over various productionsruns to make alcohol. The alcohol manufacturer may elect to offer forsale its dr-mixed ester and in doing so may also elect to represent ther-mixed ester that is sold as containing, or obtained with sources thatcontain, a recycle content.

There is also provided a use for an alcohol derived directly orindirectly from cracking r-pyoil or obtained from r-pygas, the useincluding converting r-alcohol in any synthetic process to make mixedesters.

There is also provided a use for a r-alcohol allotment or an r-olefinallotment that includes converting an alcohol in a synthetic process tomake mixed esters and applying at least a portion of an r-alcoholallotment or the r-olefin allotment to the mixed ester. An r-alcoholallotment or an r-olefin allotment is an allotment that is created bypyrolyzing recycled waste. Desirably, the allotments originate from thecracking of r-pyoil, or cracking of r-pyoil in a gas furnace, or fromr-pygas.

There is also provided a use for an acid compound by reacting an acidcompound with an r-ROH to make a mixed ester, where the r-ROH is deriveddirectly or indirectly from pyrolyzing recycled waste.

There is also provided a use for an acid by reacting the acid with analcohol to make a mixed ester, and applying at least a portion of arecycle content allotment to at least a portion of the mixed ester tomake a r-mixed ester. At least a portion of the recycle inventory fromwhich the recycle content allotment is applied to the mixed ester areallotments originating from pyrolyzing recycled waste. Desirably, theallotments originate from the cracking of r-pyoil, or cracking ofr-pyoil in a gas furnace, or from r-pygas. Also, the allotment appliedto the mixed ester can be a recycle content allotment originating frompyrolyzing recycled waste.

In one embodiment or in combination with any of the mentionedembodiments, there is also provided a use of a recycle inventory byconverting any aldehyde composition in a synthetic process to make amixed ester composition (“EC”); deducting a recycle content value fromthe recycle inventory and applying at least a portion of the deductedrecycle content value to the EC, and at least a portion of the inventorycontains a recycle content allotment. The recycle content allotment canbe present in the inventory at the time of deducting a recycle contentvalue from the recycle inventory, or a recycle content allotment depositis made into the recycle inventory before deducting a recycle contentvalue (but need not be present or accounted for when a deduction ismade), or it can be present within a year from the deduction, or withinthe same calendar year as the deduction, or within the same month as thededuction, or within the same week as the deduction. In one embodimentor in combination with any of the mentioned embodiments, the recyclecontent deduction is withdrawn against a recycle content allotment.

In one embodiment or in combination with any of the mentionedembodiments, there is provided a mixed ester composition that isobtained by any of the methods described above.

The same operator, owner, of Family of Entities may practice each ofthese steps, or one or more steps may be practiced among differentoperators, owners, or Family of Entities.

The alcohol can be stored in a storage vessel and transferred to an ECmanufacturing facility by way of truck, pipe, or ship, or as furtherdescribed below, the alcohol production facility can be integrated withthe EC facility. The alcohol may be shipped or transferred to theoperator or facility that makes the mixed ester.

In one embodiment or in combination with any of the mentionedembodiments, one may integrate two or more facilities and make r-EC. Thefacilities to make r-EC, the alcohol, the aldehyde, the olefins, and ther-pyoil and/or r-pygas, can be stand-alone facilities or facilitiesintegrated to each other. For example, one may establish a system ofproducing and consuming a recycle alcohol composition at least a portionof which is obtained from directly or indirectly from cracking r-pyoilor obtaining r-pygas; or a method of making r-EC, as follows:

-   -   a. providing an alcohol manufacturing facility that produces at        least in part an alcohol composition (“ROH”);    -   b. providing a mixed ester manufacturing facility that makes a        mixed ester composition (“EC”) and comprising a reactor        configured to accept ROH; and    -   c. feeding at least a portion of said ROH from the alcohol        manufacturing facility to the mixed ester manufacturing facility        through a supply system providing fluid communication between        said facilities;        -   wherein any one or both of the alcohol manufacturing            facility or mixed ester manufacturing facility makes or            supplies a r-ROH (r-ROH) or recycle content mixed ester            (r-EC), respectively, and optionally, wherein the alcohol            manufacturing facility supplies r-ROH to the mixed ester            manufacturing facility through the supply system.

The feeding in step c) can be a supply system providing fluidcommunication between these two facilities and capable of supplying analcohol composition from the alcohol manufacturing facility to the ECmanufacturing facility, such as a piping system that has a continuous ordiscontinuous flow.

The EC manufacturing facility can make r-EC, and can make the r-ECdirectly or indirectly from the pyrolysis of recycled waste or thecracking of r-pyoil or from r-pygas. For example, in a direct method,the EC manufacturing facility can make r-EC by accepting r-ROH from thealcohol manufacturing facility and feeding the r-aldehyde as a feedstream to a reactor to make EC. Alternatively, the EC manufacturingfacility can make r-EC by accepting any alcohol composition from thealcohol manufacturing facility and applying a recycle content to EC madewith the alcohol composition by deducting recycle content value from itsrecycle inventory and applying them to the EC, optionally in amountsusing the methods described above. The allotments obtained and stored inrecycle inventory can be obtained by any of the methods described above,and need not necessarily be allotments associated with r-ROH.

In one embodiment or in combination with any of the mentionedembodiments, there is also provided a system for producing r-EC asfollows:

-   -   a. Provide an olefin manufacturing facility configured to        produce an output composition comprising a recycle content        propylene or recycle content ethylene or both (“r-olefin”);    -   b. Optionally provide an aldehyde manufacturing facility        configured to accept an olefin stream from said olefin        manufacturing facility to produce an output composition        comprising a recycle content aldehyde (“r-AD”);    -   c. provide an ROH manufacturing facility configured to accept an        olefin stream from the olefin manufacturing facility and/or an        aldehyde stream from the aldehyde manufacturing facility and        making an output composition comprising an alcohol composition;    -   d. provide a mixed ester (EC) manufacturing facility having a        reactor configured to accept an alcohol composition and making        an output composition comprising a r-EC; and    -   e. a supply system providing fluid communication between at        least two of these facilities and capable of supplying the        output composition of one manufacturing facility to another one        or more of said manufacturing facilities.

The EC manufacturing facility can make r-EC, and can make the r-ECdirectly or indirectly from the pyrolysis of recycled waste. In thissystem, the olefin manufacturing facility can have its output in fluidcommunication with the ROH manufacturing facility which in turn can haveits output in fluid communication with the EC manufacturing facility.Alternatively, the manufacturing facilities of a) and b) alone can be influid communication, or only b) and c). In the latter case, the ECmanufacturing facility can make r-EC directly by having the r-olefinproduced in the olefin manufacturing facility converted all the way toEC, or indirectly by accepting any aldehyde composition from the ROHmanufacturing facility and applying a recycle content to EC by deductingallotments from its recycle inventory and applying them to the EC,optionally in amounts using the methods described above. The allotmentsobtained and stored in recycle inventory can be obtained by any of themethods described above, and need not necessarily be allotmentsassociated with r-aldehyde or the r-olefins. For example, the allotmentscan be obtained from any facility or source, so long as they originatefrom the pyrolysis of recycled waste, or the cracking r-pyoil orobtained from r-pygas.

The fluid communication can be gaseous, or liquid if compressed. Thefluid communication need not be continuous and can be interrupted bystorage tanks, valves, or other purification or treatment facilities, solong as the fluid can be transported from one facility to the subsequentfacility through, for example, an interconnecting pipe network andwithout the use of truck, train, ship, or airplane. For example, one ormore storage vessels may be placed in the supply system so that ther-ROH facility feeds r-ROH to a storage facility and r-ROH can bewithdrawn from the storage facility as needed by the EC manufacturingfacility, with valving and pumps and compressors utilized an in linewith the piping network as needed. Further, the facilities may share thesame site, or in other words, one site may contain two or more of thefacilities. Additionally, the facilities may also share storage tanksites, or storage tanks for ancillary chemicals, or may also shareutilities, steam or other heat sources, etc., yet also be considered asdiscrete facilities since their unit operations are separate. A facilitywill typically be bounded by a battery limit.

In one embodiment or in combination with any of the mentionedembodiments, the integrated process includes at least two facilitiesco-located within 5, or within 3, or within 2, or within 1 mile of eachother (measured as a straight line). In one embodiment or in combinationwith any of the mentioned embodiments, at least two facilities are ownedby the same Family of Entities.

In one embodiment or in combination with any of the mentionedembodiments, there is also provided an integrated r-olefin and r-ECgenerating and consumption system. This system includes:

-   -   a. provide an olefin manufacturing facility configured to        produce an output composition comprising a recycle content        propylene or recycle content ethylene or both (“r-olefin”);    -   b. optionally provide an aldehyde manufacturing facility        configured to accept an olefin stream from said olefin        manufacturing facility to produce an output composition        comprising a recycle content aldehyde (“r-AD”);    -   c. provide an ROH manufacturing facility configured to accept an        olefin stream from the olefin manufacturing facility and/or an        aldehyde stream from the aldehyde manufacturing facility and        making an output composition comprising an alcohol composition;    -   d. provide a mixed esters (CE) manufacturing facility having a        reactor configured to accept an aldehyde composition and making        an output composition comprising a r-EC; and    -   e. a piping system interconnecting at least two of said        facilities, optionally with intermediate processing equipment or        storage facilities, capable of taking off the output composition        from one facility and accept said output at any one or more of        the other facilities.

The system does not necessarily require a fluid communication betweenthe two facilities, although fluid communication is desirable. In thissystem, ethylene or propylene made at the olefin manufacturing facilitycan be delivered to the ROH facility through the interconnecting pipingnetwork that can be interrupted by other processing equipment, such astreatment, purification, pumps, compression, or equipment adapted tocombine streams, or storage facilities, all containing optionalmetering, valving, or interlock equipment. The equipment can be a fixedto the ground or fixed to structures that are fixed to the ground. Theinterconnecting piping does not need to connect to the ROH reactor orthe cracker, but rather to a delivery and receiving point at therespective facilities. The same concept applies between the ROH facilityand the EC facility. The interconnecting pipework need not connect allthree facilities to each other, but rather the interconnecting pipeworkcan be between facilities a)-b), or b)-c), or between a)-b)-c).

There can now also be provided a package or a combination of a r-EC anda recycle content identifier associated with r-EC, where the identifieris or contains a representation that the EC contains, or is sourced fromor associated with a recycle content. The package can be any suitablepackage for containing a mixed ester, such as a plastic or metal drum,railroad car, isotainer, totes, polytotes, IBC totes, bottles,jerricans, and polybags. The identifier can be a certificate document, aproduct specification stating the recycle content, a label, a logo orcertification mark from a certification agency representing that thearticle or package contains contents or the EC contains, or is made fromsources or associated with recycle content, or it can be electronicstatements by the EC manufacturer that accompany a purchase order or theproduct, or posted on a website as a statement, representation, or alogo representing that the EC contains or is made from sources that areassociated with or contain recycle content, or it can be anadvertisement transmitted electronically, by or in a website, by email,or by television, or through a tradeshow, in each case that isassociated with EC. The identifier need not state or represent that therecycle content is derived directly or indirectly from cracking r-pyoilor obtained from r-pygas. Rather, it is sufficient that the EC isdirectly or indirectly obtained at least in part from the cracking ofr-pyoil, and the identifier can merely convey or communicate that the EChas or is sourced from a recycle content, regardless of the source.

In one embodiment or in combination with any of the mentionedembodiments, there is provided a system or package comprising:

-   -   a. mixed esters (“EC”), and    -   b. an identifier (e.g. a credit, label or certification)        associated with said mixed ester, said identifier being a        representation that said mixed ester has recycle content or is        made from a source having recycle content

The system can be a physical combination, such as package having atleast EC as its contents and the package has a label, such as a logo,that the contents such as the EC has or is sourced from a recyclecontent. Alternatively, the label or certification can be issued to athird party or customer as part of a standard operating procedure of anentity whenever it transfers or sells EC having or sourced from recyclecontent. The identifier does not have to be physically on the EC or on apackage, and does not have to be on any physical document thataccompanies or is associated with the EC. For example, the identifiercan be an electronic credit or certification or representationtransferred electronically by the EC manufacturer to a customer inconnection with the sale or transfer of the EC product, and by solevirtue of being a credit, it is a representation that the EC has recyclecontent. The identifier, such as a label (such as a logo) orcertification need not state or represent that the recycle content isderived directly or indirectly from cracking r-pyoil or obtained fromr-pygas. Rather, it is sufficient that the EC is directly or indirectlyobtained at least in part either (i) from pyrolyzing recycled waste or(ii) from a recycle inventory into which at least a portion of thedeposits or credits in the recycle inventory have their origin inpyrolyzing recycled waste. The identifier itself need only convey orcommunicate that the EC has or is sourced from a recycle content,regardless of the source. In one embodiment or in combination with anyof the mentioned embodiments, articles made from the EC may have theidentifier, such as a stamp or logo embedded or adhered to the article.In one embodiment or in combination with any of the mentionedembodiments, the identifier is an electronic recycle content credit fromany source. In one embodiment or in combination with any of thementioned embodiments, the identifier is an electronic recycle contentcredit derived directly or indirectly from pyrolyzing recycled waste.

In one embodiment or in combination with any of the mentionedembodiments, the r-EC, or articles made thereby, can be offered for saleor sold as EC containing or obtained with, or an article containing orobtained with, recycle content. The sale or offer for sale can beaccompanied with a certification or representation of the recyclecontent claim made in association with the EC or article made with theEC.

The obtaining of an allocation and designating (whether internally suchas through a bookkeeping or a recycle inventory tracking softwareprogram or externally by way of declaration, certification, advertising,representing, etc.) can be by the EC manufacturer or within the ECmanufacturer Family of Entities. The designation of at least a portionof the EC as corresponding to at least a portion of the allotment (e.g.allocation or credit) can occur through a variety of means and accordingto the system employed by the EC manufacturer, which can vary frommanufacturer to manufacturer. For example, the designation can occurinternally merely through a log entry in the books or files of the ECmanufacturer or other inventory software program, or through anadvertisement or statement on a specification, on a package, on theproduct, by way of a logo associated with the product, by way of acertification declaration sheet associated with a product sold, orthrough formulas that compute the amount deducted from recycle inventoryrelative to the amount of recycle content applied to a product.

Optionally, the EC can be sold. In one embodiment or in combination withany of the mentioned embodiments, there is provided a method of offeringto sell or selling mixed esters by:

-   -   a. converting an alcohol composition in a synthetic process to        make mixed ester composition (“EC”),    -   b. applying a recycle content value to at least a portion of the        EC to thereby obtain a recycle EC (“r-EC”), and    -   c. offering to sell or selling the r-EC as having a recycle        content or obtained or derived from recycled waste.

An EC manufacturer or its Family of Entities can obtain a recyclecontent allocation, and the allocation can be obtained by any of themeans described herein and can be deposited into recycle inventory, therecycle content allocation derived directly or indirectly from thepyrolysis of recycled waste. The alcohol converted in a syntheticprocess to make a mixed ester composition can be any alcohol compositionobtained from any source, including a non-r-ROH composition, or it canbe a r-alcohol composition. The r-EC sold or offered for sale can bedesignated (e.g. labelled or certified or otherwise associated) ashaving a recycle content value. In one embodiment or in combination withany of the mentioned embodiments, at least a portion of the recyclecontent value associated with the r-EC can be drawn from a recycleinventory. In another embodiment, at least a portion of the recyclecontent value in the EC is obtained by converting r-ROH. The recyclecontent value deducted from the recycle inventory can be a non-pyrolysisrecycle content value or can be a pyrolysis recycle content allocation;i.e. a recycle content value that has its origin in pyrolysis ofrecycled waste. The recycle inventory can optionally contain at leastone entry that is an allocation derived directly or indirectly frompyrolysis of recycled waste. The designation can be the amount ofallocation deducted from recycle inventory, or the amount of recyclecontent declared or determined by the EC manufacturer in its accounts.The amount of recycle content does not necessarily have to be applied tothe EC product in a physical fashion. The designation can be an internaldesignation to or by the EC manufacturer or its Family of Entities or aservice provider in contractual relationship to the EC manufacturer orits Family of Entities. The amount of recycle content represented ascontained in the EC sold or offered for sale has a relationship orlinkage to the designation. The amount of recycle content can be a 1:1relationship in the amount of recycle content declared on an EC offeredfor sale or sold and the amount of recycle content assigned ordesignated to the EC by the EC manufacturer.

The steps described need not be sequential, and can be independent fromeach other. For example, the steps a) and b) can be simultaneous, suchas would be the case if employs a r-ROH composition to make the EC sincethe r-ROH is both an alcohol composition and has a recycle contentallocation associated with it; or where the process of making EC iscontinuous and the application of the EC application of the recyclecontent value occurs during the manufacture of EC.

EXAMPLES Abbreviations

Comp is comparative; Ex is example(s); ° C. is degree(s) Celsius; g isgram(s); mg is milligram(s); cP is centipoise;r-Pyoil Ex 1-4

Table 1 shows the composition of r-pyoil samples by gas chromatography.The r-pyoil samples produced the material from waste high and lowdensity polyethylene, polypropylene, and polystyrene. Sample 4 was alab-distilled sample in which hydrocarbons greater than C21 wereremoved. The boiling point curves of these materials are shown in FIGS.13-16 .

TABLE 1 Gas Chromatography Analysis of r-Pyoil Examples r-Pyoil FeedExamples Components 1 2 3 4 Propene 0.00 0.00 0.00 0.00 Propane 0.000.19 0.20 0.00 1,3-Butadiene 0.00 0.93 0.99 0.31 Pentene 0.16 0.37 0.390.32 Pentane 1.81 3.21 3.34 3.05 1,3-cyclopentadiene 0.00 0.00 0.00 0.002-methyl-Pentene 1.53 2.11 2.16 2.25 2-methyl-Pentane 2.04 2.44 2.483.03 Hexane 1.37 1.80 1.83 2.10 2-methyl-1,3-cyclopentadiene 0.00 0.000.00 0.00 1-methyl-1,3-cyclopentadiene 0.00 0.00 0.00 0.00 2,4dimethylpentene 0.32 0.18 0.18 0.14 Benzene 0.00 0.16 0.16 0.005-methyl-1,3-cyclopentadiene 0.00 0.17 0.17 0.20 Heptene 1.08 1.15 1.151.55 Heptane 2.51 0.17 2.89 3.61 Toluene 0.58 1.05 1.09 0.844-methylheptane 1.50 1.67 1.68 1.99 Octene 1.37 1.35 1.37 1.88 Octane2.56 2.72 2.78 3.40 2,4-dimethylheptene 1.25 1.54 1.55 1.602,4-dimethylheptane 5.08 4.01 4.05 6.40 Ethylbenzene 1.85 3.10 3.12 2.52m,p-xylene 0.73 0.69 0.24 0.90 Styrene 0.40 0.13 1.13 0.53 o-xylene 0.120.36 0.00 0.00 Nonane 2.66 2.81 2.84 3.47 Nonene 1.12 0.00 0.00 1.65MW140 2.00 1.76 1.75 2.50 Cumene 0.56 0.96 0.97 0.73Decene/methylstyrene 1.29 1.17 1.18 1.60 Decane 3.14 3.23 3.25 3.90Unknown 1 0.68 0.71 0.72 0.80 Indene 0.18 0.20 0.21 0.22 Indane 0.230.34 0.26 0.26 C11 Alkene 1.50 1.32 1.33 1.77 C11 Alkane 3.30 3.30 3.333.88 C12 Alkene 1.49 1.30 0.00 0.09 Naphthalene 0.10 0.12 3.24 3.73 C12Alkane 3.34 3.21 1.31 1.66 C13 Alkane 3.20 2.90 2.97 3.40 C13 Alkene1.46 1.20 1.17 1.53 2-methylnaphthalene 0.86 0.63 0.64 0.85 C14 Alkene1.07 0.84 0.84 1.04 C14 Alkane 3.34 3.04 3.05 3.24 Acenaphthene 0.310.28 0.28 0.28 C15 Alkene 1.16 0.87 0.87 0.96 C15 Alkane 3.41 3.00 3.022.84 C16 Alkene 0.85 0.58 0.58 0.56 C16 Alkane 3.25 2.67 2.68 2.12 C17Alkene 0.70 0.46 0.46 0.35 C17 Alkane 3.04 2.43 2.44 1.50 C18 Alkene0.51 0.33 0.33 0.19 C18 Alkane 2.71 2.11 2.13 0.99 C19 Alkane 2.39 1.820.38 0.15 C19 Alkene 0.60 0.38 1.83 0.61 C20 Alkene 0.42 0.18 0.26 0.00C20 Alkane 2.05 1.55 1.55 0.37 C21 Alkene 0.31 0.00 0.00 0.00 C21 Alkane1.72 1.45 1.30 0.23 C22 Alkene 0.00 0.00 0.00 0.00 C22 Alkane 1.43 1.111.12 0.00 C23 Alkene 0.00 0.00 0.00 0.00 C23 Alkane 1.09 0.87 0.88 0.00C24 Alkene 0.00 0.00 0.00 0.00 C24 Alkane 0.82 0.72 0.72 0.00 C25 Alkene0.00 0.00 0.00 0.00 C25 Alkane 0.61 0.58 0.56 0.00 C26 Alkene 0.00 0.000.00 0.00 C26 Alkane 0.44 0.47 0.44 0.00 C27 Alkane 0.31 0.37 0.32 0.00C28 Alkane 0.22 0.29 0.23 0.00 C29 Alkane 0.16 0.22 0.15 0.00 C30 Alkane0.00 0.16 0.00 0.00 C31 Alkane 0.00 0.00 0.00 0.00 C32 Alkane 0.00 0.000.00 0.00 Unidentified 13.73 18.59 15.44 15.91 Percent C8+ 74.86 67.5067.50 66.69 Percent C15+ 28.17 22.63 22.25 10.87 Percent Aromatics 5.918.02 11.35 10.86 Percent Paraffins 59.72 54.85 54.19 51.59 Percent C4 toC7 11.41 13.72 16.86 17.40r-Pyoil Ex 5-10

Six r-pyoil compositions were prepared by distillation of r-pyoilsamples. They were prepared by processing the material according theprocedures described below.

Ex 5. r-Pyoil with at Least 90% Boiling by 350° C., 50% Boiling Between95° C. and 200° C., and at Least 10% Boiling by 60° C.

A 250 g sample of r-pyoil from Ex 3 was distilled through a 30-trayglass Oldershaw column fitted with glycol chilled condensers,thermowells containing thermometers, and a magnet operated refluxcontroller regulated by electronic timer. Batch distillation wasconducted at atmospheric pressure with a reflux rate of 1:1. Liquidfractions were collected every 20 mL, and the overhead temperature andmass recorded to construct the boiling curve presented in FIG. 17 . Thedistillation was repeated until approximately 635 g of material wascollected.

Ex 6. r-Pyoil with at Least 90% Boiling by 150° C., 50% Boiling Between80° C. and 145° C., and at Least 10% Boiling by 60° C.

A 150 g sample of r-pyoil from Ex 3 was distilled through a 30-trayglass Oldershaw column fitted with glycol chilled condensers,thermowells containing thermometers, and a magnet operated refluxcontroller regulated by electronic timer. Batch distillation wasconducted at atmospheric pressure with a reflux rate of 1:1. Liquidfractions were collected every 20 mL, and the overhead temperature andmass recorded to construct the boiling curve presented in FIG. 18 . Thedistillation was repeated until approximately 200 g of material wascollected.

Ex 7. r-Pyoil with at Least 90% Boiling by 350° C., at Least 10% by 150°C., and 50% Boiling Between 220° C. and 280° C.

A procedure similar to Ex 8 was followed with fractions collected from120° C. to 210° C. at atmospheric pressure and the remaining fractions(up to 300° C., corrected to atmospheric pressure) under 75 torr vacuumto give a composition of 200 g with a boiling point curve described byFIG. 19 .

Ex 8. r-Pyoil with 90% Boiling Between 250-300° C.

Approximately 200 g of residuals from Ex 6 were distilled through a20-tray glass Oldershaw column fitted with glycol chilled condensers,thermowells containing thermometers, and a magnet operated refluxcontroller regulated by electronic timer. One neck of the base pot wasfitted with a rubber septum, and a low flow N₂ purge was bubbled intothe base mixture by means of an 18″ long, 20-gauge steel thermometer.Batch distillation was conducted at 70 torr vacuum with a reflux rate of1:2. Temperature measurement, pressure measurement, and timer controlwere provided by a Camille Laboratory Data Collection System. Liquidfractions were collected every 20 mL, and the overhead temperature andmass recorded. Overhead temperatures were corrected to atmosphericboiling point by means of the Clausius-Clapeyron Equation to constructthe boiling curve presented in FIG. 20 below. Approximately 150 g ofoverhead material was collected.

Ex 9. r-Pyoil with 50% Boiling Between 60-80° C.

A procedure similar to Ex 5 was followed with fractions collectedboiling between 60° C. and 230° C. to give a composition of 200 g with aboiling point curve described by FIG. 21 .

Ex 10. r-Pyoil with High Aromatic Content.

A 250 g sample of r-pyoil with high aromatic content was distilledthrough a 30-tray glass Oldershaw column fitted with glycol chilledcondensers, thermowells containing thermometers, and a magnet operatedreflux controller regulated by electronic timer. Batch distillation wasconducted at atmospheric pressure with a reflux rate of 1:1. Liquidfractions were collected every 10-20 mL, and the overhead temperatureand mass recorded to construct the boiling curve presented in FIG. 22 .The distillation ceased after approximately 200 g of material werecollected. The material contains 34 weight percent aromatic content bygas chromatography analysis.

Table 2 shows the composition of Ex 5-10 by gas chromatography analysis.

TABLE 2 Gas Chromatography Analysis of r-Pyoil Ex 5-10. r-Pyoil ExamplesComponents 5 6 7 8 9 10 Propene 0.00 0.00 0.00 0.00 0.00 0.00 Propane0.00 0.10 0.00 0.00 0.00 0.00 1,3-r-Butadiene 0.27 1.69 0.00 0.00 0.000.18 Pentene 0.44 1.43 0.00 0.00 0.00 0.48 Pentane 3.95 4.00 0.00 0.000.37 4.59 Unknown 1 0.09 0.28 0.00 0.00 0.00 0.07 1,3-cyclopentadiene0.00 0.13 0.00 0.00 0.00 0.00 2-methyl-Pentene 2.75 3.00 0.00 0.00 5.794.98 2-methyl-Pentane 2.63 6.71 0.00 0.00 9.92 5.56 Hexane 0.75 4.770.00 0.00 11.13 3.71 2-methyl-1,3-cyclopentadiene 0.00 0.20 0.00 0.000.96 0.30 1-methyl-1,3-cyclopentadiene 0.00 0.00 0.00 0.00 0.00 0.00 2,4dimethylpentene 0.00 0.35 0.00 0.00 2.06 0.26 Benzene 0.00 0.24 0.000.00 1.11 0.26 5-methyl-1,3-cyclopentadiene 0.00 0.09 0.00 0.00 0.150.15 Heptene 0.52 5.50 0.00 0.00 6.22 2.97 Heptane 0.13 7.35 0.17 0.0010.16 6.85 Toluene 1.18 2.79 0.69 0.00 2.39 6.98 4-methylheptane 2.542.46 3.29 0.00 1.16 3.92 Octene 3.09 4.72 2.50 0.00 0.48 2.62 Octane5.77 6.27 3.49 0.00 0.65 4.50 2,4-dimethylheptene 3.92 2.30 0.61 0.000.96 2.58 2,4-dimethylheptane 9.47 5.80 1.30 0.00 3.74 0.00 Ethylbenzene0.00 0.00 1.32 0.00 2.43 7.81 m,p-xylene 7.48 4.36 0.23 0.00 1.09 15.18Styrene 0.90 1.80 0.40 0.00 2.32 1.47 o-xylene 0.28 0.00 0.12 0.00 0.000.00 Nonane 3.74 5.94 0.41 0.00 6.15 2.55 Nonene 1.45 3.87 0.84 0.002.53 1.14 MW140 2.36 1.94 1.63 0.00 3.69 2.35 Cumene 1.30 1.23 0.54 0.002.13 2.43 Decene/methylstyrene 1.54 1.60 1.55 0.00 0.30 0.48 Decane 4.311.68 4.34 0.00 0.48 1.08 Unknown 2 0.96 0.15 0.97 0.00 0.00 0.24 Indene0.25 0.00 0.21 0.00 0.00 0.00 Indane 0.33 0.00 0.33 0.00 0.00 0.08 C11Alkene 1.83 0.22 1.83 0.00 0.00 0.19 C11 Alkane 4.54 0.18 4.75 0.00 0.000.39 C12 Alkene 1.68 0.08 2.34 0.00 0.18 0.08 Naphthalene 0.09 0.00 0.110.00 0.00 0.00 C12 Alkane 4.28 0.09 6.14 0.00 0.84 0.16 C13 Alkane 4.110.00 6.80 3.32 0.68 0.08 C13 Alkene 1.67 0.00 2.85 0.38 0.37 0.002-methylnaphthalene 0.70 0.00 0.00 0.93 0.14 0.00 C14 Alkene 0.08 0.001.81 3.52 0.00 0.00 C14 Alkane 0.14 0.09 6.20 14.12 0.00 0.00Acenaphthylene 0.00 0.00 0.75 0.00 0.00 0.00 C15 Alkene 0.00 0.00 2.703.55 0.00 0.00 C15 Alkane 0.00 0.09 9.40 14.16 0.00 0.07 C16 Alkene 0.000.00 1.61 2.20 0.00 0.00 C16 Alkane 0.00 0.10 5.44 12.40 0.00 0.00 C17Alkene 0.00 0.00 0.10 3.35 0.00 0.00 C17 Alkane 0.00 0.10 0.26 16.810.00 0.00 C18 Alkene 0.00 0.00 0.00 0.67 0.00 0.00 C18 Alkane 0.00 0.100.00 3.31 0.00 0.00 C19 Alkane 0.00 0.00 0.00 0.13 0.00 0.00 C19 Alkene0.00 0.00 0.00 0.00 0.00 0.00 C20 Alkene 0.00 0.00 0.00 0.00 0.00 0.00C20 Alkane 0.00 0.00 0.00 0.00 0.00 0.00 C21 Alkene 0.00 0.00 0.00 0.000.00 0.00 Unidentified 18.51 16.18 21.95 21.13 19.45 13.24 Percent C4-C712.71 38.55 0.85 0.00 50.25 37.35 Percent C8+ 68.78 45.17 77.20 78.8730.30 49.41 Percent C15+ 0.00 0.38 19.52 56.60 0.00 0.07 PercentAromatics 14.04 12.02 6.27 0.93 11.90 34.70 Percent Paraffins 52.3559.75 55.64 64.26 56.08 44.89Ex 11-58 Involving Steam Cracking r-Pyoil in a Lab Unit.

The invention is further illustrated by the following steam crackingexamples. Examples were performed in a laboratory unit to simulate theresults obtained in a commercial steam cracker. A drawing of the labsteam cracker is shown in FIG. 11 . Lab Steam Cracker 910 consisted of asection of ⅜ inch Incoloy™ tubing 912 that was heated in a 24-inchApplied Test Systems three zone furnace 920. Each zone (Zone 1 922 a,Zone 2 922 b, and Zone 3 922 c) in the furnace was heated by a 7-inchsection of electrical coils. Thermocouples 924 a, 924 b, and 924 c werefastened to the external walls at the mid-point of each zone fortemperature control of the reactor. Internal reactor thermocouples 926 aand 926 b were also placed at the exit of Zone 1 and the exit of Zone 2,respectively. The r-pyoil source 930 was fed through line 980 to Iscosyringe pump 990 and fed to the reactor through line 981 a. The watersource 940 was fed through line 982 to ICSO syringe pump 992 and fed topreheater 942 through line 983 a for conversion to steam prior toentering the reactor in line 981 a with pyoil. A propane cylinder 950was attached by line 984 to mass flow controller 994. The plant nitrogensource 970 was attached by line 988 to mass flow controller 996. Thepropane or nitrogen stream was fed through line 983 a to preheater 942to facilitate even steam generation prior to entering the reactor inline 981 a. Quartz glass wool was placed in the 1 inch space between thethree zones of the furnace to reduce temperature gradients between them.In an optional configuration, the top internal thermocouple 922 a wasremoved for a few examples to feed r-pyoil either at the mid-point ofZone 1 or at the transition between Zone 1 and Zone 2 through a sectionof ⅛ inch diameter tubing. The dashed lines in FIG. 11 show the optionalconfigurations. A heavier dashed line extends the feed point to thetransition between Zone 1 and Zone 2. Steam was also optionally added atthese positions in the reactor by feeding water from Isco syringe pump992 through the dashed line 983 b. r-Pyoil, and optionally steam, werethen fed through dashed line 981 b to the reactor. Thus, the reactor canbe operated be feeding various combinations of components and at variouslocations. Typical operating conditions were heating the first zone to600° C., the second zone to about 700° C., and the third zone to 375° C.while maintaining 3 psig at the reactor exit. Typical flow rates ofhydrocarbon feed and steam resulted in a 0.5 sec residence time in one7-inch section of the furnace. The first 7-inch section of the furnace922 a was operated as the convection zone and the second 7-inch section922 b as the radiant zone of a steam cracker. The gaseous effluent ofthe reactor exited the reactor through line 972. The stream was cooledwith shell and tube condenser 934 and any condensed liquids werecollected in glycol cooled sight glass 936. The liquid material wasremoved periodically through line 978 for weighing and gaschromatography analysis. The gas stream was fed through line 976 a forventing through a back-pressure regulator that maintained about 3 psigon the unit. The flow rate was measured with a Sensidyne GilianGilibrator-2 Calibrator. Periodically a portion of the gas stream wassent in line 976 b to a gas chromatography sampling system for analysis.The unit could be was operated in a decoking mode by physicallydisconnecting propane line 984 and attaching air cylinder 960 with line986 and flexible tubing line 974 a to mass flow controlled 994.

Analysis of reaction feed components and products was done by gaschromatography. All percentages are by weight unless specifiedotherwise. Liquid samples were analyzed on an Agilent 7890A using aRestek RTX-1 column (30 meters×320 micron ID, 0.5 micron film thickness)over a temperature range of 35° C. to 300° C. and a flame ionizationdetector. Gas samples were analyzed on an Agilent 8890 gaschromatograph. This GC was configured to analyze refinery gas up to C₆with H₂S content. The system used four valves, three detectors, 2 packedcolumns, 3 micro-packed columns, and 2 capillary columns. The columnsused were the following: 2 ft× 1/16 in, 1 mm i.d. HayeSep A 80/100 meshUltiMetal Plus 41 mm; 1.7 m× 1/16 in, 1 mm i.d. HayeSep A 80/100 meshUltiMetal Plus 41 mm; 2 m× 1/16 in, 1 mm i.d. MolSieve 13×80/100 meshUltiMetal Plus 41 mm; 3 ft×⅛ in, 2.1 mm i.d. HayeSep Q 80/100 mesh inUltiMetal Plus; 8 ft×⅛ in, 2.1 mm i.d. Molecular Sieve 5A 60/80 mesh inUltiMetal Plus; 2 m×0.32 mm, 5 um thickness DB-1 (123-1015, cut); 25m×0.32 mm, 8 um thickness HP-AL/S (19091P-S12). The FID channel wasconfigured to analyze the hydrocarbons with the capillary columns fromC₁ to C₅, while C₆/C₆₊ components are backflushed and measured as onepeak at the beginning of the analysis. The first channel (reference gasHe) was configured to analyze fixed gases (such as CO₂, CO, O₂, N₂, andH₂S). This channel was run isothermally, with all micro-packed columnsinstalled inside a valve oven. The second TCD channel (third detector,reference gas N₂) analyzed hydrogen through regular packed columns. Theanalyses from both chromatographs were combined based on the mass ofeach stream (gas and liquid where present) to provide an overall assayfor the reactor.

A typical run was made as follows:

Nitrogen (130 sccm) was purged through the reactor system, and thereactor was heated (zone 1, zone 2, zone 3 setpoints 300° C., 450° C.,300° C., respectively). Preheaters and cooler for post-reactor liquidcollection were powered on. After 15 minutes and the preheater was above100° C., 0.1 mL/min water was added to the preheater to generate steam.The reactor temperature setpoints were raised to 450° C., 600° C., and350° C. for zones 1, 2, and 3, respectively. After another 10 min, thereactor temperature setpoints were raised to 600° C., 700° C., and 375°C. for zones 1, 2, and 3, respectively. The N₂ was decreased to zero asthe propane flow was increased to 130 sccm. After 100 min at theseconditions either r-pyoil or r-pyoil in naphtha was introduced, and thepropane flow was reduced. The propane flow was 104 sccm, and the r-pyoilfeed rate was 0.051 g/hr for a run with 80% propane and 20% r-pyoil.This material was steam cracked for 4.5 hr (with gas and liquidsampling). Then, 130 sccm propane flow was reestablished. After 1 hr,the reactor was cooled and purged with nitrogen.Steam Cracking with r-Pyoil Ex 1.

Table 3 contains examples of runs made in the lab steam cracker withpropane, r-pyoil from Ex 1, and various weight ratios of the two. Steamwas fed to the reactor in a 0.4 steam to hydrocarbon ratio in all runs.Nitrogen (5% by weight relative to the hydrocarbon) was fed with steamin the run with only r-pyoil to aid in even steam generation. Comp Ex 1is an example involving cracking only propane.

TABLE 3 Steam Cracking Examples using r-pyoil from Ex 1. Comp Ex #s Ex 111 12 13 14 15 Zone 2 Control Temp 700 700 700 700 700 700    Propane(wt %) 100 85 80 67 50 0   r-Pyoil (wt %) 0 15 20 33 50 100*    Feed Wt,g/hr 15.36 15.43 15.35 15.4 15.33 15.35  Steam/Hydrocarbon Ratio 0.4 0.40.4 0.4 0.4 0.4  Total Accountability, % 103.7 94.9 94.5 89.8 87.7 86   Total Products Wt % C6+ 1.15 2.61 2.62 4.38 7.78 26.14  methane 18.0418.40 17.68 17.51 17.52 12.30  ethane 2.19 2.59 2.46 2.55 2.88 2.44ethylene 30.69 32.25 31.80 32.36 32.97 23.09  propane 24.04 19.11 20.2516.87 11.66 0.33 propylene 17.82 17.40 17.63 16.80 15.36 7.34 i-butane0.00 0.04 0.04 0.03 0.03 0.01 n-butane 0.03 0.02 0.02 0.02 0.02 0.02propydiene 0.07 0.14 0.13 0.15 0.17 0.14 acetylene 0.24 0.40 0.40 0.450.48 0.41 t-2-butene 0.00 0.19 0.00 0.00 0.00 0.11 1-butene 0.16 0.850.19 0.19 0.20 0.23 i-butylene 0.92 0.34 0.87 0.81 0.66 0.81 c-2-butene0.12 0.15 0.40 0.56 0.73 0.11 i-pentane 0.13 0.00 0.00 0.00 0.00 0.00n-pentane 0.00 0.01 0.01 0.02 0.02 0.02 1,3-butadiene 1.73 2.26 2.312.63 3.02 2.88 methyl acetylene 0.20 0.26 0.26 0.30 0.32 0.28t-2-pentene 0.11 0.08 0.12 0.12 0.12 0.05 2-methyl-2-butene 0.02 0.010.03 0.03 0.02 0.02 1-pentene 0.05 0.09 0.01 0.02 0.02 0.03 c-2-pentene0.06 0.01 0.03 0.03 0.03 0.01 pentadiene 1 0.00 0.01 0.02 0.02 0.02 0.08pentadiene 2 0.01 0.04 0.04 0.05 0.06 0.16 pentadiene 3 0.12 0.21 0.230.27 0.30 0.26 1,3-Cyclopentadiene 0.48 0.85 0.81 1.01 1.25 1.58pentadiene 4 0.00 0.08 0.08 0.09 0.10 0.07 pentadiene 5 0.06 0.17 0.170.20 0.23 0.31 CO2 0.00 0.00 0.00 0.00 0.00 0.00 CO 0.12 0.11 0.05 0.000.12 0.74 hydrogen 1.40 1.31 1.27 1.21 1.13 0.67 Unidentified 0.00 0.000.10 1.33 2.79 19.37  Olefin/Aromatics Ratio 45.42 21.07 20.91 12.627.11 1.42 Total Aromatics 1.15 2.61 2.62 4.38 7.78 26.14  Propylene +Ethylene 48.51 49.66 49.43 49.16 48.34 30.43  Ethylene/Propylene Ratio1.72 1.85 1.80 1.93 2.15 3.14 *5% N2 was also added to facilitate steamgeneration. Analysis has been normalized to exclude it.

As the amount of r-pyoil used is increased relative to propane, therewas an increase in the formation of dienes. For example, bothr-butadiene and cyclopentadiene increased as more r-pyoil is added tothe feed. Additionally, aromatics (C6+) increased considerably withincreased r-pyoil in the feed.

Accountability decreased with increasing amounts of r-pyoil in theseexamples. It was determined that some r-pyoil in the feed was being heldup in the preheater section. Due to the short run times, accountabilitywas negatively affected. A slight increase in the slope of the reactorinlet line corrected the issue (see Ex 24). Nonetheless, even with anaccountability of 86% in Ex 15, the trend was clear. The overall yieldof r-ethylene and r-propylene decreased from about 50% to less thanabout 35% as the amount of r-pyoil in the feed increased. Indeed,feeding r-pyoil alone produced about 40% of aromatics (C6+) andunidentified higher boilers (see Ex 15 and Ex 24).

r-Ethylene Yield—r-Ethylene yield showed an increase from 30.7% to >32%as 15% r-pyoil was co-cracked with propane. The yield of r-ethylene thenremained about 32% until >50% r-pyoil was used. With 100% r-pyoil, theyield of r-ethylene decreased to 21.5% due to the large amount ofaromatics and unidentified high boilers (>40%). Since r-pyoil cracksfaster than propane, a feed with an increased amount of r-pyoil willcrack faster to more r-propylene. The r-propylene can then react to formr-ethylene, diene and aromatics. When the concentration of r-pyoil wasincreased the amount of r-propylene cracked products was also increased.Thus, the increased amount of dienes can react with other dienes andolefins (like r-ethylene) leading to even more aromatics formation. So,at 100% r-pyoil in the feed, the amount of r-ethylene and r-propylenerecovered was lower due to the high concentration of aromatics thatformed. In fact, the olefin/aromatic dropped from 45.4 to 1.4 as r-pyoilwas increased to 100% in the feed. Thus, the yield of r-ethyleneincreased as more r-pyoil was added to the feed mixture, at least toabout 50% r-pyoil. Feeding pyoil in propane provides a way to increasethe ethylene/propylene ratio on a steam cracker.

r-Propylene Yield—r-Propylene yield decreased with more r-pyoil in thefeed. It dropped from 17.8% with propane only to 17.4% with 15% r-pyoiland then to 6.8% as 100% r-pyoil was cracked. r-Propylene formation didnot decrease in these cases. r-Pyoil cracks at lower temperature thanpropane. As r-propylene is formed earlier in the reactor it has moretime to converted to other materials—like dienes and aromatics andr-ethylene. Thus, feeding r-pyoil with propane to a cracker provides away to increase the yield of ethylene, dienes and aromatics.

The r-ethylene/r-propylene ratio increased as more r-pyoil was added tothe feed because an increase concentration of r-pyoil made r-propylenefaster, and the r-propylene reacted to other cracked products likedienes, aromatics and r-ethylene.

The ethylene to propylene ratio increased from 1.72 to 3.14 going from100% propane to 100% r-pyoil cracking. The ratio was lower for 15%r-pyoil (0.54) than 20% r-pyoil (0.55) due to experimental error withthe small change in r-pyoil feed and the error from having just one runat each condition.

The olefin/aromatic ratio decreased from 45 with no r-pyoil in the feedto 1.4 with no propane in the feed. The decrease occurred mainly becauser-pyoil cracked more readily than propane and thus more r-propylene wasproduced faster. This gave the r-propylene more time to react further—tomake more r-ethylene, dienes, and aromatics. Thus, aromatics increased,and r-propylene decreased with the olefin/aromatic ratio decreasing as aresult.

r-Butadiene increased as the concentration of r-pyoil in the feedincreased, thus providing a way to increase r-butadiene yield.r-Butadiene increased from 1.73% with propane cracking, to about 2.3%with 15-20% r-pyoil in the feed, to 2.63% with 33% r-pyoil, and to 3.02%with 50% r-pyoil. The amount was 2.88% at 100% r-pyoil. Ex 24 showed3.37% r-butadiene observed in another run with 100% r-pyoil. This amountmay be a more accurate value based on the accountability problems thatoccurred in Ex 15. The increase in r-butadiene was the result of moreseverity in cracking as products like r-propylene continued to crack toother materials.

Cyclopentadiene increased with increasing r-pyoil except for thedecrease in going from 15%-20% r-pyoil (from 0.85 to 0.81). Again, someexperimental error was likely. Thus, cyclopentadiene increased from0.48% cracking propane only, to about 0.85% at 15-20% r-pyoil in thereactor feed, to 1.01% with 33% r-pyoil, to 1.25 with 50% r-pyoil, and1.58% with 100% r-pyoil. The increase in cyclobutadiene was also theresult of more severity in cracking as products like r-propylenecontinued to crack to other materials. Thus, cracking r-pyoil withpropane provided a way to increase cyclopentadiene production.

Operating with r-pyoil in the feed to the steam cracker resulted in lesspropane in the reactor effluent. In commercial operation, this wouldresult in a decreased mass flow in the recycle loop. The lower flowwould decrease cryogenic energy costs and potentially increase capacityon the plant if it is capacity constrained. Additionally, lower propanein the recycle loop would debottleneck the r-propylene fractionator ifit is already capacity limited. Steam Cracking with r-Pyoil Ex 1-4.

Table 4 contains examples of runs made with the r-pyoil samples found inTable 1 with a propane/r-pyoil weight ratio of 80/20 and 0.4 steam tohydrocarbon ratio.

TABLE 4 Examples using r-PyOil Ex 1-4 under similar conditions. Ex # 1617 18 19 r-Pyoil from Table 1 1 2 3 4 Zone 2 Control Temp 700 700 700700 Propane (wt %) 80 80 80 80 r-Pyoil (wt %) 20 20 20 20 N₂ (wt %) 0 00 0 Feed Wt, g/hr 15.35 15.35 15.35 15.35 Steam/Hydrocarbon Ratio 0.40.4 0.4 0.4 Total Accountability, % 94.5 96.4 95.6 95.3 Total ProductsWt % C6+ 2.62 2.86 3.11 2.85 methane 17.68 17.36 17.97 17.20 ethane 2.462.55 2.67 2.47 ethylene 31.80 30.83 31.58 30.64 propane 20.25 21.5419.34 21.34 propylene 17.63 17.32 17.18 17.37 i-butane 0.04 0.04 0.040.04 n-butane 0.02 0.01 0.02 0.03 propadiene 0.13 0.06 0.09 0.12acetylene 0.40 0.11 0.26 0.37 t-2-butene 0.00 0.00 0.00 0.00 1-butene0.19 0.19 0.20 0.19 i-butylene 0.87 0.91 0.91 0.98 c-2-butene 0.40 0.440.45 0.52 i-pentane 0.00 0.14 0.16 0.16 n-pentane 0.01 0.03 0.03 0.031,3-butadiene 2.31 2.28 2.33 2.27 methyl acetylene 0.26 0.23 0.23 0.24t-2-pentene 0.12 0.13 0.14 0.13 2-methyl-2-butene 0.03 0.04 0.04 0.031-pentene 0.01 0.02 0.02 0.02 c-2-pentene 0.03 0.06 0.05 0.04 pentadiene1 0.02 0.00 0.00 0.00 pentadiene 2 0.04 0.02 0.02 0.01 pentadiene 3 0.230.17 0.00 0.25 1,3-Cyclopentadiene 0.81 0.72 0.76 0.71 pentadiene 4 0.080.00 0.00 0.00 pentadiene 5 0.17 0.08 0.09 0.08 CO₂ 0.00 0.00 0.00 0.00CO 0.05 0.00 0.00 0.00 hydrogen 1.27 1.22 1.26 1.21 Unidentified 0.100.65 1.04 0.69 Olefin/Aromatics Ratio 20.91 18.66 17.30 18.75 TotalAromatics 2.62 2.86 3.11 2.85 Propylene + Ethylene 49.43 48.14 48.7748.01 Ethylene/Propylene Ratio 1.80 1.78 1.84 1.76

Steam cracking of the different r-pyoil Ex 1-4 at the same conditionsgave similar results. Even the lab distilled sample of r-pyoil (Ex 19)cracked like the other samples. The highest r-ethylene and r-propyleneyield was for Ex 16, but the range was 48.01-49.43. Ther-ethylene/r-propylene ratio varied from 1.76 to 1.84. The amount ofaromatics (C6+) only varied from 2.62 to 3.11. Ex 16 also produced thesmallest yield of aromatics. The r-pyoil used for this example (r-PyoilEx 1, Table 1) contained the largest amount of paraffins and the lowestamount of aromatics. Both are desirable for cracking to r-ethylene andr-propylene.

Steam Cracking with r-Pyoil Ex 2.

Table 5 contains runs made in the lab steam cracker with propane (CompEx 2), r-pyoil Ex 2, and four runs with a propane/pyrolysis oil weightratio of 80/20. Comp Ex 2 and Ex 20 were run with a 0.2 steam tohydrocarbon ratio. Steam was fed to the reactor in a 0.4 steam tohydrocarbon ratio in all other examples. Nitrogen (5% by weight relativeto the r-pyoil) was fed with steam in the run with only r-pyoil (Ex 24).

TABLE 5 Examples using r-Pyoil Ex 2. Comp Ex #s Ex 2 20 21 22 23 24 Zone2 Control Temp 700° C. 700° C. 700° C. 700° C. 700° C 700° C.    Propane(wt %) 100 80 80 80 80 0   r-Pyoil (wt %) 0 20 20 20 20 100*    Feed Wt,g/hr 15.36 15.35 15.35 15.35 15.35 15.35  Steam/Hydrocarbon Ratio 0.20.2 0.4 0.4 0.4 0.4  Total Accountability, % 100.3 93.8 99.1 93.4 96.497.9  Total Products Wt % C6+ 1.36 2.97 2.53 2.98 2.86 22.54  methane18.59 19.59 17.34 16.64 17.36 11.41  ethane 2.56 3.09 2.26 2.35 2.553.00 ethylene 30.70 32.51 31.19 29.89 30.83 24.88  propane 23.00 17.2821.63 23.84 21.54 0.38 propylene 18.06 16.78 17.72 17.24 17.32 10.94 i-butane 0.04 0.03 0.03 0.05 0.04 0.02 n-butane 0.01 0.03 0.03 0.03 0.010.09 propadiene 0.05 0.10 0.12 0.12 0.06 0.12 acetylene 0.12 0.35 0.400.36 0.11 0.31 t-2-butene 0.00 0.00 0.00 0.00 0.00 0.00 1-butene 0.170.20 0.18 0.18 0.19 0.25 i-butylene 0.87 0.80 0.91 0.94 0.91 1.22c-2-butene 0.14 0.40 0.40 0.44 0.44 1.47 i-pentane 0.14 0.13 0.00 0.000.14 0.13 n-pentane 0.00 0.01 0.02 0.03 0.03 0.01 1,3-butadiene 1.742.35 2.20 2.18 2.28 3.37 methyl acetylene 0.18 0.22 0.26 0.24 0.23 0.23t-2-pentene 0.13 0.14 0.12 0.12 0.13 0.14 2-methyl-2-butene 0.03 0.040.03 0.04 0.04 0.10 1-pentene 0.01 0.03 0.01 0.01 0.02 0.05 c-2-pentene0.04 0.04 0.03 0.04 0.06 0.18 pentadiene 1 0.00 0.01 0.01 0.02 0.00 0.14pentadiene 2 0.01 0.02 0.03 0.02 0.02 0.19 pentadiene 3 0.00 0.24 0.190.24 0.17 0.50 1,3-Cyclopentadiene 0.52 0.83 0.65 0.71 0.72 1.44pentadiene 4 0.00 0.00 0.00 0.00 0.00 0.01 pentadiene 5 0.06 0.09 0.080.08 0.08 0.15 CO₂ 0.00 0.00 0.00 0.00 0.00 0.00 CO 0.07 0.00 0.00 0.000.00 0.19 hydrogen 1.36 1.28 1.28 1.21 1.22 0.63 Unidentified 0.00 0.000.34 0.00 0.65 15.89  Olefin/Aromatics Ratio 38.54 18.39 21.26 17.5518.66 2.00 Total Aromatics 1.36 2.97 2.53 2.98 2.86 22.54  Propylene +−Ethylene 48.76 49.29 48.91 47.13 48.14 35.82  Ethylene/Propylene Ratio1.70 1.94 1.76 1.73 1.78 2.27 *5% N₂ was also added to facilitate steamgeneration. Analysis has been normalized to exclude it.

Comparing Ex 20 to Ex 21-23 shows that the increased feed flow rate(from 192 sccm in Ex 20 to 255 sccm with more steam in Ex 21-23)resulted in less conversion of propane and r-pyoil due to the 25%shorter residence time in the reactor (r-ethylene and r-propylene: 49.3%for Ex 20 vs 47.1, 48.1, 48.9% for Ex 21-23). r-Ethylene was higher inEx 21 with the increased residence time since propane and r-pyoilcracked to higher conversion of r-ethylene and r-propylene and some ofthe r-propylene can then be converted to additional r-ethylene. Andconversely, r-propylene was higher in the higher flow examples with ahigher steam to hydrocarbon ratio (Ex 21-23) since it has less time tocontinue reacting. Thus, Ex 21-23 produced a smaller amount of othercomponents: r-ethylene, C6+(aromatics), r-butadiene, cyclopentadiene,etc., than found in Ex 20.

Ex 21-23 were run at the same conditions and showed that there was somevariability in operation of the lab unit, but it was sufficiently smallthat trends can be seen when different conditions are used.

Ex 24, like Ex 15, showed that the r-propylene and r-ethylene yielddecreased when 100% r-pyoil was cracked compared to feed with 20%r-pyoil. The amount decreased from about 48% (in Ex 21-23) to 36%. Totalaromatics was greater than 20% of the product as in Ex 15.

Steam Cracking with r-Pyoil Ex 3.

Table 6 contains runs made in the lab steam cracker with propane andr-pyoil Ex 3 at different steam to hydrocarbon ratios. 1

TABLE 6 Examples using r-Pyoil Ex 3. Ex # 25 26 Zone 2 Control Temp 700°C. 700° C. Propane (wt %) 80 80 r-Pyoil (wt %) 20 20 N2 (wt %) 0 0 FeedWt, g/hr 15.33 15.33 Steam/Hydrocarbon Ratio 0.4 0.2 TotalAccountability, % 95.6 92.1 Total Products Wt % C6+ 3.11 3.42 methane17.97 18.57 ethane 2.67 3.01 ethylene 31.58 31.97 propane 19.34 17.43propylene 17.18 17.17 i-butane 0.04 0.04 n-butane 0.02 0.03 propadiene0.09 0.10 acetylene 0.26 0.35 t-2-butene 0.00 0.00 1-butene 0.20 0.20i-butylene 0.91 0.88 c-2-butene 0.45 0.45 i-pentane 0.16 0.17 n-pentane0.03 0.02 1,3-butadiene 2.33 2.35 methyl acetylene 0.23 0.22 t-2-pentene0.14 0.15 2-methyl-2-butene 0.04 0.04 1-pentene 0.02 0.02 c-2-pentene0.05 0.04 pentadiene 1 0.00 0.00 pentadiene 2 0.02 0.02 pentadiene 30.00 0.25 1,3-Cyclopentadiene 0.76 0.84 pentadiene 4 0.00 0.00pentadiene 5 0.09 0.10 CO2 0.00 0.00 CO 0.00 0.00 hydrogen 1.26 1.24Unidentified 1.04 0.92 Olefin/Aromatics Ratio 17.30 15.98 TotalAromatics 3.11 3.42 Propylene + Ethylene 48.77 49.14 Ethylene/PropyleneRatio 1.84 1.86

The same trends observed from cracking with r-pyoil Ex 1-2 weredemonstrated for cracking with propane and r-pyoil Ex 3. Ex 25 comparedto Ex 26 showed that a decrease in the feed flow rate (to 192 sccm in Ex26 with less steam from 255 sccm in Ex 25) resulted in greaterconversion of the propane and r-pyoil due to the 25% greater residencetime in the reactor (r-ethylene and r-propylene: 48.77% for Ex 22 vs49.14% for the lower flow in Ex 26). r-Ethylene was higher in Ex 26 withthe increased residence time since propane and r-pyoil cracked to higherconversion of r-ethylene and r-propylene and some of the r-propylene wasthen converted to additional r-ethylene. Thus, Ex 25, with the shorterresidence time produced a smaller amount of other components:r-ethylene, C6+(aromatics), r-butadiene, cyclopentadiene, etc., thanfound in Ex 26.

Steam Cracking with r-Pyoil Ex 4.

Table 7 contains runs made in the lab steam cracker with propane andpyrolysis oil sample 4 at two different steam to hydrocarbon ratios.

TABLE 7 Examples using Pyrolysis Oil Ex 4. Ex # 27 28 Zone 2 ControlTemp 700° C. 700° C. Propane (wt %) 80 80 r-Pyoil (wt %) 20 20 N₂ (wt %)0 0 Feed Wt, g/hr 15.35 15.35 Steam/Hydrocarbon Ratio 0.4 0.6 TotalAccountability, % 95.3 95.4 Total Products wt % C6+ 2.85 2.48 methane17.20 15.37 ethane 2.47 2.09 ethylene 30.64 28.80 propane 21.34 25.58propylene 17.37 17.79 i-butane 0.04 0.05 n-butane 0.03 0.03 propadiene0.12 0.12 acetylene 0.37 0.35 t-2-butene 0.00 0.00 1-butene 0.19 0.19i-butylene 0.98 1.03 c-2-butene 0.52 0.53 i-pentane 0.16 0.15 n-pentane0.03 0.05 1,3-butadiene 2.27 2.15 methyl acetylene 0.24 0.25 t-2-pentene0.13 0.12 2-methyl-2-butene 0.03 0.04 1-pentene 0.02 0.02 c-2-pentene0.04 0.05 pentadiene 1 0.00 0.00 pentadiene 2 0.01 0.02 pentadiene 30.25 0.27 1,3-Cyclopentadiene 0.71 0.65 pentadiene 4 0.00 0.00pentadiene 5 0.08 0.08 CO2 0.00 0.00 CO 0.00 0.00 hydrogen 1.21 1.15Unidentified 0.69 0.63 Olefin/Aromatics Ratio 18.75 20.94 TotalAromatics 2.85 2.48 Propylene + Ethylene 48.01 46.59 Ethylene/PropyleneRatio 1.76 1.62

The results in Table 7 showed the same trends as discussed with Ex 20 vsEx 21-23 in Table 5 and Ex 25 vs Ex 26 in Table 6. At a smaller steam tohydrocarbon ratio, higher amounts of r-ethylene and r-propylene andhigher amounts of aromatics were obtained at the increased residencetime. The r-ethylene/r-propylene ratio was also greater.

Thus, comparing Ex 20 with Ex 21-23 in Table 5, Ex 25 with Ex 26, and Ex27 with Ex 28 showed the same effect. Decreasing the steam tohydrocarbon ratio decreased the total flow in the reactor. Thisincreased the residence time. As a result, there was an increase in theamount of r-ethylene and r-propylene produced. The r-ethylene tor-propylene ratio was larger which indicated that some r-propylenereacted to other products like r-ethylene. There was also an increase inaromatics (C6+) and dienes.

Examples of Cracking r-Pyoils from Table 2 with Propane

Table 8 contains the results of runs made in the lab steam cracker withpropane (Comp Ex 3) and the six r-pyoil samples listed in Table 2. Steamwas fed to the reactor in a 0.4 steam to hydrocarbon ratio in all runs.

Ex 30, 33, and 34 were the results of runs with r-pyoil having greaterthan 35% C4-C7. The r-pyoil used in Ex 40 contained 34.7% aromatics.Comp Ex 3 was a run with propane only. Ex 29, 31, and 32 were theresults of runs with r-pyoil containing less than 35% C4-C7.

TABLE 8 Examples of steam cracking with propane and r-pyoils. Ex # CompEx 3 29 30 31 32 33 34 r-Pyoil Feed from Table 2 5 6 7 8 9 10 Zone 2Control Temp, ° C. 700 700 700 700 700 700 700 Propane (wt %) 100 80 8080 80 80 80 r-Pyoil (wt %) 0 20 20 20 20 20 20 Feed Wt, g/hr 15.36 15.3215.33 15.33 15.35 15.35 15.35 Steam/Hydrocarbon Ratio 0.4 0.4 0.4 0.40.4 0.4 0.4 Total Accountability, % 103 100 100.3 96.7 96.3 95.7 97.3Total Products wt % C6+ 1.13 2.86 2.64 3.03 2.34 3.16 3.00 methane 17.6917.17 15.97 17.04 16.42 18.00 16.41 ethane 2.27 2.28 2.12 2.26 2.59 2.632.19 ethylene 29.85 31.03 29.23 30.81 30.73 30.80 28.99 propane 24.9021.86 25.13 21.70 23.79 20.99 24.57 propylene 18.11 17.36 17.78 17.2318.08 17.90 17.32 i-butane 0.05 0.04 0.05 0.04 0.05 0.04 0.05 n-butane0.02 0.02 0.04 0.02 0.00 0.00 0.02 propadiene 0.08 0.14 0.12 0.14 0.040.04 0.10 acetylene 0.31 0.42 0.36 0.42 0.04 0.06 0.31 t-2-butene 0.000.00 0.00 0.00 0.00 0.00 0.00 1-butene 0.16 0.18 0.19 0.18 0.19 0.200.18 i-butylene 0.91 0.93 1.00 0.92 0.93 0.90 0.95 c-2-butene 0.13 0.510.50 0.50 0.34 0.68 0.61 i-pentane 0.14 0.00 0.15 0.00 0.16 0.16 0.15n-pentane 0.00 0.04 0.05 0.04 0.00 0.00 0.06 1,3-butadiene 1.64 2.282.15 2.26 2.48 2.23 2.04 methyl acetylene 0.19 0.28 0.24 0.28 n/a 0.240.24 t-2-pentene 0.12 0.12 0.12 0.12 0.13 0.13 0.11 2-methyl-2-butene0.03 0.03 0.03 0.03 0.04 0.03 0.03 1-pentene 0.11 0.02 0.02 0.02 0.010.02 0.02 c-2-pentene 0.01 0.03 0.04 0.03 0.11 0.10 0.05 pentadiene 10.00 0.02 0.00 0.02 0.00 0.00 0.00 pentadiene 2 0.01 0.03 0.03 0.04 0.010.05 0.02 pentadiene 3 0.14 0.25 0.00 0.25 0.00 0.00 0.001,3-Cyclopentadiene 0.44 0.77 0.69 0.77 0.22 0.30 0.63 pentadiene 4 0.000.00 0.00 0.00 0.00 0.00 0.00 pentadiene 5 0.06 0.08 0.08 0.08 0.09 0.080.07 CO2 0.00 0.00 0.00 0.00 0.00 0.00 0.00 CO 0.11 0.00 0.07 0.00 0.000.00 0.11 hydrogen 1.36 1.26 1.21 1.25 1.18 1.25 1.22 unidentified 0.000.00 0.00 0.52 0.00 0.00 0.56 Olefin/Aromatics Ratio 45.81 18.79 19.6617.64 22.84 16.91 17.06 Total Aromatics 1.13 2.86 2.64 3.03 2.34 3.163.00 Propylene + Ethylene 47.96 48.39 47.01 48.04 48.82 48.70 46.31Ethylene/Propylene Ratio 1.65 1.79 1.64 1.79 1.70 1.72 1.67

The examples in Table 8 involved using an 80/20 mix of propane with thevarious distilled r-pyoils. The results were like those in previousexamples involving cracking r-pyoil with propane. All the examplesproduced an increase in aromatics and dienes relative to crackingpropane only. As a result, the olefins to aromatic ratio was lower forcracking the combined feeds. The amount of r-propylene and r-ethyleneproduced was 47.01-48.82% for all examples except for the 46.31%obtained with the r-pyoil with 34.7% aromatic content (using r-pyoil Ex10 in Ex 34). Except for that difference, the r-pyoils performedsimilarly, and any of them can be fed with C-2 to C-4 in a steamcracker. r-Pyoils having high aromatic content like r-pyoil Ex 10 maynot be the preferred feed for a steam cracker, and a r-pyoil having lessthan about 20% aromatic content should be considered a more preferredfeed for co-cracking with ethane or propane.

Example of Steam Cracking r-Pyoils from Table 2 with Natural Gasoline.

Table 9 contains the results of runs made in the lab steam cracker witha natural gasoline sample from a supplier and the r-pyoils listed inTable 2. The natural gasoline material was greater than 99% C5-C8 andcontained greater than 70% identified paraffins and about 6% aromatics.The material had an initial boiling point of 100° F., a 50% boilingpoint of 128° F., a 95% boiling point of 208° F., and a final boilingpoint of 240° F. No component greater than C9 were identified in thenatural gasoline sample. It was used as a typical naphtha stream for theexamples.

The results presented in Table 9 include examples involving cracking thenatural gasoline (Comp Ex 4), or cracking a mixture of natural gasolineand the r-pyoil samples listed in Table 2. Steam was fed to the reactorin a 0.4 steam to hydrocarbon ratio in all runs. Nitrogen (5% by weightrelative to the hydrocarbon) was fed with water to facilitate even steamgeneration. Ex 35, 37, and 38 involved runs with r-pyoils containingvery little C15+. Ex 38 illustrated the results of a run with greaterthan 50% C15+ in the r-pyoil.

The gas flow of the reactor effluent and the gas chromatography analysisof the stream were used to determine the weight of gas product, and thenthe weight of other liquid material needed for 100% accountability wascalculated. This liquid material was typically 50-75% aromatics, andmore typically 60-70%. An actual assay of the liquid sample wasdifficult for these examples. The liquid product in most of theseexamples was an emulsion that was hard to separate and assay. Since thegas analysis was reliable, this method allowed an accurate comparison ofthe gaseous products while still having an estimate of the liquidproduct if it was completely recovered.

TABLE 9 Results of Cracking r-Pyoil with Natural Gasoline. Ex # Comp Ex4 35 36 37 38 39 40 r-Pyoil Feed from Table 2 Natural Gasoline 5 6 7 8 910 Zone 2 Control Temp 700    700    700    700    700    700    700   Natural Gasoline (wt %) 100    80    80    80    80    80    80   r-Pyoil (wt %) 0   20    20    20    20    20    20    N2 (wt %) 5*  5*   5*   5*   5*   5*   5*   Feed Wt, g/hr 15.4  15.3  15.4  15.4 15.4  15.4  15.4  Gas Exit Flow, sccm 221.2   206.7   204.5   211.8  211.3   202.6   207.8   Gas Weight Accountability, % 92.5  83.1  81.5 79.9  83.9  81.7  84.3  Total Products Wt % C6+ 9.54 7.86 6.32 8.05 7.237.15 5.75 methane 19.19  18.33  16.98  17.80  19.46  17.88  15.67 ethane 3.91 3.91 3.24 3.86 4.02 3.52 2.77 ethylene 27.34  26.14  28.24 24.96  27.74  26.42  29.39  propane 0.42 0.40 0.38 0.36 0.37 0.37 0.42propylene 12.97  12.49  13.61  10.87  11.80  12.34  16.10  i-butane 0.030.03 0.03 0.02 0.02 0.02 0.03 n-butane 0.11 0.07 0.00 0.05 0.00 0.050.00 propadiene 0.22 0.18 0.10 0.18 0.08 0.22 0.11 acetylene 0.40 0.340.11 0.33 0.09 0.41 0.13 t-2-butene 0.00 0.00 0.00 0.00 0.00 0.00 0.001-butene 0.44 0.39 0.40 0.32 0.38 0.39 0.46 i-butylene 0.91 0.89 0.910.65 0.76 0.86 1.30 c-2-butene 2.98 2.85 2.98 2.28 2.58 2.94 3.58i-pentane 0.08 0.03 0.02 0.05 0.04 0.03 0.02 n-pentane 5.55 1.95 0.842.21 1.72 1.45 1.33 1,3-butadiene 3.17 3.09 3.77 2.94 3.54 3.48 3.78methyl acetylene 0.37 0.32 0.40 0.31 0.36 0.39 n/a t-2-pentene 0.14 0.120.12 0.12 0.14 0.12 0.12 2-methyl-2-butene 0.07 0.06 0.04 0.07 0.08 0.070.06 1-pentene 0.10 0.08 0.08 0.09 0.11 0.10 0.09 c-2-pentene 0.20 0.170.07 0.19 0.12 0.09 0.08 pentadiene 1 0.35 0.12 0.02 0.19 0.13 0.09 0.06pentadiene 2 0.80 0.52 0.16 0.59 0.54 0.40 0.29 pentadiene 3 0.48 0.100.00 0.46 0.00 0.00 0.00 1,3-Cyclopentadiene 1.03 1.00 0.56 0.98 0.561.09 0.56 pentadiene 4 0.00 0.00 0.00 0.00 0.00 0.00 0.00 pentadiene 50.11 0.11 0.13 0.10 0.13 0.12 0.00 CO2 0.01 0.00 0.00 0.00 0.00 0.000.00 CO 0.00 0.00 0.10 0.00 0.00 0.06 0.13 hydrogen 1.00 0.92 0.94 0.870.95 0.93 1.03 Other High Boilers- calculated** 8.09 17.54  19.45 21.12  17.06  19.01  16.75  C6+ and Other Calculated High Boilers 17.63 25.40  25.77  29.17  24.28  26.17  22.50  Ethylene and Propylene 40.31 38.63  41.86  35.83  39.54  38.76  45.48  Ethylene/Propylene Ratio 2.112.09 2.07 2.30 2.35 2.14 1.83 Olefin/Aromatics in gas effluent 5.38 6.158.10 5.59 6.74 6.81 9.74 *5% Nitrogen was also added to facilitate steamgeneration. Analysis has been normalized to exclude it. **Calculatedtheoretical amount needed for 100% accountability based on the actualreactor effluent gas flow rate and gas chromatography analysis.

The cracking examples in Table 9 involved using an 80/20 mix of naturalgasoline with the various distilled r-pyoils. The natural gasoline andr-pyoils examples produced an increase in C6+(aromatics), unidentifiedhigh boilers, and dienes relative to cracking propane only or r-pyoiland propane (see Table 8). The increase in aromatics in the gas phasewas about double compared to cracking 20% by weight r-pyoil withpropane. Since the liquid product was typically greater than 60%aromatics, the total amount of aromatics was probably 5 times greaterthan cracking 20% by weight r-pyoil with propane. The amount ofr-propylene and r-ethylene produced was generally lower by about 10%.The r-ethylene and r-propylene yield ranged from 35.83-41.86% for allexamples except for the 45.48% obtained with high aromatic r-pyoil(using Ex 10 material in Ex 40). This is almost in the range of theyields obtained from cracking r-pyoil and propane (46.3-48.8% in Table7). Ex 40 produced the highest amount of r-propylene (16.1%) and thehighest amount of r-ethylene (29.39%). This material also produced thelowest r-ethylene/r-propylene ratio which suggests that there was lessconversion of r-propylene to other products than in the other examples.This result was unanticipated. The high concentration of aromatics(34.7%) in the r-pyoil feed appeared to inhibit further reaction ofr-propylene. It is thought that r-pyoils having an aromatic content of25-50% will see similar results. Co-cracking this material with naturalgasoline also produced the lowest amount of C6+ and unidentified highboilers, but this stream produced the most r-butadiene. The naturalgasoline and r-pyoil both cracked easier than propane so the r-propylenethat formed reacted to give the increase in r-ethylene, aromatics,dienes, and others. Thus, the r-ethylene/r-propylene ratio was above 2in all these examples, except in Ex 40. The ratio in this example (1.83)was similar to the 1.65-1.79 range observed in Table 8 for crackingr-pyoil and propane. Except for these differences, the r-pyoilsperformed similarly and any of them can be fed with naphtha in a steamcracker.

Steam Cracking r-Pyoil with Ethane

Table 10 shows the results of cracking ethane and propane alone, andcracking with r-pyoil Ex 2. The examples from cracking either ethane orethane and r-pyoil were operated at three Zone 2 control temperatures:700° C., 705° C., and 710° C.

TABLE 10 Examples of Cracking Ethane and r-pyoil at differenttemperatures. Comp Comp Comp Comp Comp Ex # Ex 5 41 Ex 6 42 Ex 7 43 Ex 3Ex 8 Zone 2 Control Temp 700° C. 700° C. 705° C. 705° C. 710° C. 710° C.700° C. 700° C. Propane or Ethane in Feed Ethane Ethane Ethane EthaneEthane Ethane Propane Propane Propane or Ethane (wt %) 100 80 100 80 10080 100 80 r-Pyoil (wt %) 0 20 0 20 0 20 0 20 Feed Wt, g/hr 10.48 10.4710.48 10.47 10.48 10.47 15.36 15.35 Steam/Hydrocarbon Ratio 0.4 0.4 0.40.4 0.4 0.4 0.4 0.4 Total Accountability, % 107.4 94.9 110.45 97.0 104.496.8 103.0 96.4 Total Products Wt % C6+ 0.22 1.42 0.43 2.18 0.64 2.791.13 2.86 methane 1.90 6.41 2.67 8.04 3.69 8.80 17.69 17.36 ethane 46.3639.94 38.75 33.77 32.15 26.82 2.27 2.55 ethylene 44.89 44.89 51.27 48.5355.63 53.41 29.85 30.83 propane 0.08 0.18 0.09 0.18 0.10 0.16 24.9021.54 propylene 0.66 2.18 0.84 1.99 1.03 1.86 18.11 17.32 i-butane 0.000.00 0.00 0.00 0.00 0.00 0.05 0.04 n-butane 0.00 0.00 0.00 0.00 0.000.00 0.02 0.01 propadiene 0.41 0.26 0.37 0.22 0.31 0.19 0.08 0.06acetylene 0.00 0.01 0.00 0.01 0.00 0.01 0.31 0.11 t-2-butene 0.00 0.000.00 0.00 0.00 0.00 0.00 0.00 1-butene 0.04 0.07 0.05 0.07 0.06 0.070.16 0.19 i-butylene 0.00 0.15 0.00 0.15 0.00 0.14 0.91 0.91 c-2-butene0.12 0.19 0.13 0.11 0.13 0.08 0.13 0.44 i-pentane 0.59 0.05 0.04 0.060.05 0.06 0.14 0.14 n-pentane 0.01 0.01 0.00 0.00 0.00 0.00 0.00 0.031,3-butadiene 0.96 1.45 1.34 1.69 1.72 2.06 1.64 2.28 methyl acetylenen/a n/a n/a n/a n/a n/a 0.19 0.23 t-2-pentene 0.03 0.04 0.02 0.04 0.030.05 0.12 0.13 2-methyl-2-butene 0.02 0.00 0.03 0.00 0.03 0.00 0.03 0.041-pentene 0.00 0.00 0.00 0.00 0.00 0.00 0.11 0.02 c-2-pentene 0.03 0.040.03 0.04 0.03 0.03 0.01 0.06 pentadiene 1 0.00 0.00 0.00 0.00 0.00 0.000.00 0.00 pentadiene 2 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.02pentadiene 3 0.00 0.00 0.00 0.00 0.00 0.00 0.14 0.17 1,3-Cyclopentadiene0.03 0.06 0.02 0.05 0.02 0.05 0.44 0.72 pentadiene 4 0.00 0.00 0.00 0.000.00 0.00 0.00 0.00 pentadiene 5 0.00 0.03 0.00 0.03 0.00 0.03 0.06 0.08CO2 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 CO 0.00 0.00 0.00 0.00 0.000.00 0.11 0.00 hydrogen 3.46 2.66 3.94 2.90 4.36 3.43 1.36 1.22unidentified 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.65 Olefin/Aromatics216.63 34.87 126.61 24.25 91.78 20.80 45.81 18.66 Total Aromatics 0.221.42 0.43 2.18 0.64 2.79 1.13 2.86 Propylene + Ethylene 45.56 47.0752.11 50.52 56.65 55.28 47.96 48.14 Ethylene/Propylene Ratio 67.53 20.5960.95 24.44 54.13 28.66 1.65 1.78

A limited number of runs with ethane were made. As can be seen in theComp Ex 5-7 and Comp Ex 3, conversion of ethane to products occurredmore slowly than with propane. Comp Ex 5 with ethane and Comp Ex 3 withpropane were run at the same molar flow rates and temperatures. However,conversion of ethane was only 52% (100%—46% ethane in product) vs 75%for propane. However, the r-ethylene/r-propylene ratio was much higher(67.53 vs 1.65) as ethane cracking produced mainly r-ethylene. Theolefin to aromatics ratio for ethane cracking was also much higher forethane cracking. The Comp Ex 5-7 and Ex 41-43 compare cracking ethane toan 80/20 mixture of ethane and r-pyoil at 700° C., 705° C. and 710° C.Production of total r-ethylene plus r-propylene increased with bothethane feed and the combined feed when the temperature was increased (anincrease from about 46% to about 55% for both). Although the r-ethyleneto r-propylene ratio decreased for ethane cracking with increasingtemperature (from 67.53 at 700° C. to 60.95 at 705° C. to 54.13 at 710°C.), the ratio increased for the mixed feed (from 20.59 to 24.44 to28.66). r-Propylene was produced from the r-pyoil and some continued tocrack generating more cracked products such as r-ethylene, dienes andaromatics. The amount of aromatics in propane cracking with r-pyoil at700° C. (2.86% in Comp Ex 8) was about the same as cracking ethane andr-pyoil at 710° C. (2.79% in Ex 43).

Co-cracking ethane and r-pyoil required higher temperature to obtainmore conversion to products compared to co-cracking with propane andr-pyoil. Ethane cracking produced mainly r-ethylene. Since a hightemperature was required to crack ethane, cracking a mixture of ethaneand r-pyoil produced more aromatics and dienes as some r-propylenereacted further. Operation in this mode would be appropriate ifaromatics and dienes were desired with minimal production ofr-propylene.

Examples of Cracking r-Pyoil and Propane 5° C. Higher or Lower thanCracking Propane.

Table 11 contains runs made in the lab steam cracker with propane at695° C., 700° C., and 705° C. (Comp Ex 3, 9-10) and Ex 44-46 using 80/20propane/r-pyoil weight ratios at these temperatures. Steam was fed tothe reactor in a 0.4 steam to hydrocarbon ratio in all runs. r-Pyoil Ex2 was cracked with propane in these examples.

TABLE 11 Examples using r-Pyoil Ex 2 at 700° C. +/− 5° C. Comp Comp CompEx # Ex 9 Ex 3 Ex 10 44 45 46 Zone 2 Control Temp, ° C. 695 700 705 695700 705 Propane (wt %) 100 100 100 80 80 80 r-Pyoil Ex 2 (wt %) 0 0 0 2020 20 Zone 2 Exit Temp, ° C. 683 689 695 685 691 696 Feed Wt, g/hr 15.3615.36 15.36 15.35 15.35 15.35 Steam/Hydrocarbon Ratio 0.4 0.4 0.4 0.40.4 0.4 Total Accountability, % 105 103 100.2 99.9 96.4 94.5 TotalProducts Wt % C6+ 0.76 1.13 1.58 2.44 2.86 4.02 methane 15.06 17.6920.02 14.80 17.36 19.33 ethane 1.92 2.27 2.49 2.20 2.55 2.63 ethylene25.76 29.85 33.22 27.14 30.83 33.06 propane 33.15 24.90 18.96 28.2121.54 15.38 propylene 18.35 18.11 16.61 17.91 17.32 15.43 i-butane 0.050.05 0.03 0.06 0.04 0.03 n-butane 0.02 0.02 0.02 0.03 0.01 0.02propadiene 0.07 0.08 0.10 0.10 0.06 0.12 acetylene 0.22 0.31 0.42 0.270.11 0.47 t-2-butene 0.00 0.00 0.00 0.00 0.00 0.00 1-butene 0.15 0.160.16 0.19 0.19 0.17 i-butylene 0.95 0.91 0.80 1.01 0.91 0.72 c-2-butene0.11 0.13 0.13 0.49 0.44 0.33 i-pentane 0.12 0.14 0.13 0.15 0.14 0.12n-pentane 0.00 0.00 0.00 0.02 0.03 0.02 1,3-butadiene 1.22 1.64 2.001.93 2.28 2.39 methyl acetylene 0.14 0.19 0.23 0.20 0.23 0.26t-2-pentene 0.11 0.12 0.12 0.12 0.13 0.12 2-methyl-2-butene 0.02 0.030.02 0.04 0.04 0.03 1-pentene 0.11 0.11 0.05 0.02 0.02 0.01 c-2-pentene0.01 0.01 0.06 0.04 0.06 0.03 pentadiene 1 0.00 0.00 0.00 0.01 0.00 0.00pentadiene 2 0.00 0.01 0.01 0.01 0.02 0.01 pentadiene 3 0.12 0.14 0.160.24 0.17 0.22 1,3-Cyclopentadiene 0.30 0.44 0.59 0.59 0.72 0.83pentadiene 4 0.00 0.00 0.00 0.00 0.00 0.00 pentadiene 5 0.05 0.06 0.060.07 0.08 0.08 CO2 0.00 0.00 0.00 0.00 0.00 0.00 CO 0.00 0.11 0.47 0.000.00 0.00 hydrogen 1.21 1.36 1.50 1.09 1.22 1.32 unidentified 0.00 0.000.00 0.61 0.65 2.84 Olefin/Aromatics Ratio 62.38 45.81 34.23 20.43 18.6613.33 Total Aromatics 0.76 1.13 1.58 2.44 2.86 4.02 Propylene + Ethylene44.12 47.96 49.83 45.05 48.14 48.49 Ethylene/Propylene Ratio 1.40 1.652.00 1.52 1.78 2.14

Operating at a higher temperature in the propane tube gave a higherconversion of propane—mainly to r-ethylene and r-propylene (increasingfrom 44.12% to 47.96% to 49.83% in Comp Ex 9, 3, and 10 respectively).The higher the temperature the more r-ethylene was produced at theexpense of r-propylene (r-ethylene/r-propylene ratio increased from 1.40to 1.65 to 2.0 in Comp Ex 9, 3, and 10). Aromatics also increased withhigher temperature. The same trends were observed with cracking themixed streams in Ex 44-46: increased r-ethylene and r-propylene from45.05% to 48.49%), increased r-ethylene/r-propylene ratio (from 1.52 to2.14), and an increase in total aromatics (from 2.44% to 4.02%). It isknown that r-pyoil conversion to cracked products is greater at a giventemperature relative to propane.

For the condition where the mixed feed has a 5° C. lower reactor outlettemperature consider the following two cases:

Case A. Comp Ex 3 (Propane at 700° C.) and Ex 441 (80/20 at 695° C.)

Case B. Comp Ex 103 (Propane at 705° C.) and Ex 452 (80/20 at 700° C.)

Operating the combined tube at 5° C. lower temperature allowed isolationof more r-propylene relative to the higher temperature. For example,operating at 700° C. in Ex 45 vs 705° C. in Ex 46, r-propylene was17.32% vs 15.43%. Similarly, operating at 695° C. in Ex 44 vs 700° C. inEx 45, r-propylene was 17.91% vs 17.32%. r-Propylene and r-ethyleneyield increased as temperature was increased, but this occurred at theexpense of r-propylene as shown by the increasing r-ethylene tor-propylene ratio (from 1.52 at 695° C. in Ex 44 to 2.14 at 705° C. inEx 46). The ratio also increased for propane feed, but it started from aslightly lower level. Here, the ratio increased from 1.40 at 695° C. to2.0 at 705° C.

The lower temperature in the combined tube still gave almost as goodconversion to r-ethylene and r-propylene (For Case A: 47.96% for propanecracking vs 45.05% for combined cracking and for Case B: 49.83% forpropane cracking vs 48.15% combined). Operation of the combined tube atlower temperature also decreased aromatics and dienes. Thus, this modeis preferred if more r-propylene is desired relative to r-ethylene whileminimizing production of C6+(aromatics) and dienes.

For the condition where the mixed tube has a 5° C. higher reactor outlettemperature, consider the following two cases:

Case A. Comp Ex 3 (Propane at 700° C. and Ex 46 (80/20 at 705° C.)

Case B. Comp Ex 9 (Propane at 695° C.) and Ex 45 (80/20 at 700° C.)

Running lower temperature in the propane tube decreased the conversionof propane and decreased the r-ethylene to r-propylene ratio. The ratiowas lower at lower temperatures for both the combined feed and thepropane feed cases. The r-pyoil conversion to cracked products wasgreater at a given temperature relative to propane. It was seen thatoperating 5° C. higher in the combined tube caused production of morer-ethylene and less r-propylene relative to the lower temperature. Thismode—with the higher temperature in the combined tube—gave an increasedconversion to r-ethylene plus r-propylene (For Case A: 47.96% forpropane cracking in Comp Ex 3 vs 48.49% in Ex 46 for combined cracking,and for Case B: 44.11% for propane cracking (Comp Ex 9) vs 48.15% forcombined cracking (Ex 45) at 5° C. higher temperature).

Operation in this mode (5° C. higher temperature in the combined tube)increases production of r-ethylene, aromatics, and dienes, if sodesired. By operating the propane tube at a lower temperature—whichoperates at a lower ethylene to propylene ratio—the r-propyleneproduction can be maintained compared to running both tubes at the sametemperature. For example, operating the combined tube at 700° C. and thepropane tube at 695° C. resulted in 18.35% and 17.32%, respectively, ofr-propylene. Running both at 695° C. would give 0.6% more r-propylene inthe combined tube. Thus, this mode is preferred if more aromatics,dienes, and slightly more r-ethylene is desired while minimizingproduction loss of r-propylene.

The temperatures were measured at the exit of Zone 2 which is operatedto simulate the radiant zone of the cracking furnace. These temperaturesare shown in Table 11. Although there were considerable heat loses inoperating a small lab unit, the temperatures showed that the exittemperatures for the combined feed cases were 1-2° C. higher than forthe corresponding propane only feed case. Steam cracking is anendothermic process. There is less heat needed in cracking with pyoiland propane than when cracking propane alone, and thus the temperaturedoes not decrease as much.

Examples Feeding r-Pyoil or r-Pyoil and Steam at Various Locations.

Table 12 contains runs made in the lab steam cracker with propane andr-pyoil Ex 3. Steam was fed to the reactor in a 0.4 steam to hydrocarbonratio in all runs. r-Pyoil and steam were fed at different locations(see configurations in FIG. 11 ). In Ex 48, the reactor inlettemperature was controlled at 380° C., and r-pyoil was fed as a gas. Thereactor inlet temperature was usually controlled at 130-150° C. whenr-pyoil was fed as a liquid (Ex 49) in the typical reactorconfiguration.

TABLE 12 Examples with r-Pyoil and Steam Fed at Different Locations. Ex#* 47 48 49 50 51 52 Zone 2 Control Temp 700° C. 700° C. 700° C. 700° C.700° C. 700° C. Propane (wt %) 80 80 80 80 80 80 r-Pyoil (wt %) 20 20 2020 20 20 Feed Wt, g/hr 15.33 15.33 15.33 15.33 15.33 15.33Steam/hydrocarbon ratio 0.4 0.4 0.4 0.4 0.4 0.4 Total Accountability, %95.8 97.1 97.83 97.33 96.5 97.3 Total Products Wt % C6+ 3.03 3.66 4.503.32 3.03 3.38 methane 17.37 18.49 19.33 17.46 19.85 17.38 ethane 2.583.04 3.27 2.60 3.18 2.35 ethylene 30.30 31.07 31.53 30.93 32.10 30.75propane 21.90 19.10 16.57 20.11 17.79 21.96 propylene 16.82 16.78 15.9717.24 16.64 16.14 i-butane 0.04 0.04 0.03 0.04 0.03 0.04 n-butane 0.040.03 0.03 0.03 0.03 0.03 propadiene 0.10 0.09 0.09 0.11 0.11 0.12acetylene 0.35 0.33 0.33 0.36 0.34 0.40 t-2-butene 0.00 0.00 0.00 0.000.00 0.00 1-butene 0.19 0.19 0.19 0.19 0.18 0.18 i-butylene 0.94 0.790.72 0.86 0.73 0.86 c-2-butene 0.43 0.39 0.39 0.43 0.37 0.39 i-pentane0.16 0.16 0.16 0.16 0.15 0.15 n-pentane 0.04 0.02 0.02 0.03 0.02 0.041,3-butadiene 2.15 2.16 2.22 2.28 2.20 2.29 methyl acetylene 0.21 0.210.20 0.23 0.22 0.24 t-2-pentene 0.13 0.13 0.13 0.13 0.12 0.122-methyl-2-butene 0.04 0.03 0.03 0.03 0.03 0.03 1-pentene 0.02 0.01 0.020.02 0.02 0.02 c-2-pentene 0.05 0.03 0.03 0.03 0.03 0.04 pentadiene 10.00 0.00 0.01 0.00 0.00 0.00 pentadiene 2 0.03 0.02 0.02 0.02 0.01 0.01pentadiene 3 0.25 0.07 0.22 0.24 0.22 0.24 1,3-Cyclopentadiene 0.72 0.760.83 0.80 0.79 0.81 pentadiene 4 0.00 0.00 0.00 0.00 0.00 0.00pentadiene 5 0.08 0.08 0.08 0.08 0.08 0.08 CO₂ 0.00 0.00 0.00 0.00 0.050.00 CO 0.00 0.00 0.00 0.00 0.23 0.00 hydrogen 1.24 1.23 1.23 1.21 1.421.25 Unidentified 0.79 1.09 1.80 1.06 0.00 0.71 Olefin/Aromatics Ratio17.27 14.36 11.67 16.08 17.71 15.43 Total Aromatics 3.03 3.66 4.50 3.323.03 3.38 Propylene + Ethylene 47.12 47.85 47.50 48.17 48.75 46.89Ethylene/Propylene Ratio 1.80 1.85 1.97 1.79 1.93 1.91 *Ex 47 -r-Pyoilfed between zone 1 and zone 2: Proxy For Crossover *Ex 48- r-Pyoil andsteam fed between zone 1 and zone 2: Proxy for Crossover *Ex 49- r-Pyoiland steam fed at midpoint of zone 1: Proxy for Downstream of Inlet *Ex50- r-Pyoil fed at midpoint of zone 1: Proxy for Downstream of Inlet *Ex51- r-Pyoil fed as gas at inlet of zone 1 *Ex 49- r-Pyoil fed as liquidat inlet of zone 1

Feeding propane and r-pyoil as a gas at reactor inlet (Ex 51) gave ahigher conversion to r-ethylene and r-propylene compared to Ex 52 wherethe r-pyoil was fed as a liquid. Some conversion was due to heating thestream to near 400° C. where some cracking occurred. Since the r-pyoilwas vaporized outside the reactor, no heat supplied for that purpose wasrequired by the furnace. Thus, more heat was available for cracking. Asa result, a greater amount of r-ethylene and r-propylene (48.75%) wasobtained compared to that obtained when the r-pyoil was fed as a liquidat the top of the reactor (46.89% in Ex 52). Additionally, r-pyoilentering the reactor as a gas decreased residence time in the reactorwhich resulted in lower total aromatics and an increasedolefin/aromatics ratio for Ex 51.

In the other examples (Ex 47-50) either r-pyoil or r-pyoil and steam wasfed at the simulated crossover between the convection zone and theradiant zone of a steam cracking furnace (between Zone 1 and Zone 2 ofthe lab furnace) or at the mid-point of Zone 1. There was littledifference in the cracking results except for the aromatic content in Ex49. Feeding r-pyoil and steam at the midpoint of Zone 1 resulted in thegreatest amount of aromatics. The number of aromatics was also high whensteam was cofed with r-pyoil between Zone 1 and Zone 2 (Ex 48). Bothexamples had a longer overall residence time for propane to react beforethe streams were combined compared to the other Examples in the table.Thus, the particular combination of longer residence time for crackingpropane and a slightly shorter residence time for r-pyoil cracking in Ex49 resulted in a greater amount of aromatics as cracked products.

Feeding r-pyoil as a liquid at the top of reactor (Ex 52) gave thelowest conversion of all the conditions. This was due to the r-pyoilrequiring vaporization which needed heat. The lower temperature in Zone1 resulted in less cracking when compared to Ex 51.

Higher conversion to r-ethylene and r-propylene was obtained by feedingthe r-pyoil at the crossover or the midpoint of the convection sectionfor one main reason. The propane residence time in the top of thebed—before introduction of r-pyoil or r-pyoil and steam—was lower. Thus,propane can achieve higher conversion to r-ethylene and r-propylenerelative to Ex 52 with a 0.5 sec residence time for the entire feedstream. Feeding propane and r-pyoil as a gas at reactor inlet (Ex 51)gave the highest conversion to r-ethylene and r-propylene because noneof the furnace heat was used in vaporization of r-pyoil as was requiredfor the other examples.

Decoking Examples from Cracking r-Pyoil Ex 5 with Propane or NaturalGasoline.

Propane was cracked at the same temperature and feed rate as an 80/20mixture of propane and r-pyoil from Ex 5 and an 80/20 mixture of naturalgasoline and r-pyoil from Ex 5. All examples were operated in the sameway. The examples were run with a Zone 2 control temperature of 700° C.When the reactor was at stable temperature, propane was cracked for 100min, followed by 4.5 hr of cracking propane, or propane and r-pyoil, ornatural gasoline and r-pyoil, followed by another 60 min of propanecracking. The steam/hydrocarbon ratio was varied in these comparativeexamples from 0.1 to 0.4. The propane cracking results are shown inTable 13 as Comp Ex 11-13. The results presented in Table 14 includeexamples (Ex 53-58) involving cracking an 80/20 mixture of propane ornatural gasoline with r-pyoil from Ex 5 at different steam tohydrocarbon ratios. Nitrogen (5% by weight relative to the hydrocarbon)was fed with steam in the examples with natural gasoline and r-pyoil toprovide even steam generation. In the examples involving crackingr-pyoil with natural gasoline, the liquid samples were not analyzed.Rather, the measured reactor effluent gas flow rate and gaschromatography analysis were used to calculate the theoretical weight ofunidentified material for 100% accountability.

Following each steam cracking run, decoking of the reactor tube wasperformed. Decoking involved heating all three zones of the furnace to700° C. under 200 sccm N₂ flow and 124 sccm steam. Then, 110 sccm airwas introduced to bring the oxygen concentration to 5%. Then, the airflow was slowly increased to 310 sccm as the nitrogen flow was decreasedover two hours. Next, the furnace temperature was increased to 825° C.over two hours. These conditions were maintained for 5 hours. Gaschromatography analysis were performed every 15 minutes beginning withthe introduction of the air stream. The amount of carbon was calculatedbased on the amount of CO₂ and CO in each analysis. The amount of carbonwas totalized until no CO was observed, and the amount of CO₂ was lessthan 0.05%. The results (mg carbon by gas chromatography analysis) fromdecoking the propane comparative examples are found in Table 13. Theresults from the r-pyoil examples is found in Table 14.

TABLE 13 Comparative Examples of Cracking with Propane. Ex # Comp Ex 11Comp Ex 12 Comp Ex 13 Zone 2 Control Temp,° C. 700° C. 700° C. 700° C.Propane (wt %) 100 100 100 r-Pyoil (wt %) 0 0 0 N2 (wt %) 0 0 0 Feed Wt,g/hr 15.36 15.36 15.36 Steam/Hydrocarbon Ratio 0.1 0.2 0.4 TotalAccountability, % 98.71 101.30 99.96 Total Products Wt % C6+ 1.71 1.441.10 Methane 20.34 19.92 17.98 Ethane 3.04 2.83 2.25 Ethylene 32.4832.29 30.43 Propane 19.04 20.26 24.89 Propylene 17.72 17.88 18.19i-butane 0.04 0.04 0.04 n-butane 0.03 0.00 0.00 Propadiene 0.08 0.040.04 Acetylene 0.31 0.03 0.04 t-2-butene 0.00 0.00 0.00 1-butene 0.180.18 0.17 i-butylene 0.78 0.82 0.93 c-2-butene 0.15 0.14 0.13 i-pentane0.15 0.15 0.14 n-pentane 0.00 0.00 0.00 1,3-butadiene 1.93 1.90 1.68methyl acetylene 0.18 0.18 0.19 t-2-pentene 0.14 0.14 0.122-methyl-2-butene 0.03 0.03 0.03 1-pentene 0.01 0.01 0.01 c-2-pentene0.01 0.11 0.10 pentadiene 1 0.00 0.00 0.00 pentadiene 2 0.01 0.01 0.01pentadiene 3 0.00 0.00 0.00 1,3-Cyclopentadiene 0.17 0.16 0.14pentadiene 4 0.00 0.00 0.00 pentadiene 5 0.07 0.00 0.01 CO₂ 0.00 0.000.00 CO 0.00 0.00 0.00 Hydrogen 1.41 1.43 1.39 Unidentified 0.00 0.000.00 Olefin/Aromatics Ratio 31.53 37.20 47.31 Total Aromatics 1.71 1.441.10 Propylene + Ethylene 50.20 50.17 48.62 Ethylene/Propylene Ratio1.83 1.81 1.67 Carbon from Decoking, mg 16 51 1.5

TABLE 14 Examples of Cracking Propane or Natural Gasoline and r-Pyoil.Ex # 53 54 55 56 57 58 Propane or Natural Gasoline Propane PropanePropane Nat Gas Nat Gas Nat Gas Zone 2 Control Temp 700 700 700 700   700    700    Propane/Nat Gas (wt %) 80 80 80 80    80    80    r-Pyoil(wt %) 20 20 20 20    20    20    N2 (wt %) 0 0 0 5*   5*   5*   FeedWt, g/hr 15.32 15.32 15.32 15.29  15.29  15.29  Steam/Hydrocarbon Ratio0.1 0.2 0.4 0.4  0.6  0.7  Total Accountability, % 95.4 99.4 97.5100**   100**   100**   Total Products Wt % C6+ 2.88 2.13 2.30 5.69 4.975.62 Methane 18.83 16.08 16.62 15.60  16.81  18.43  Ethane 3.56 2.852.27 2.97 3.43 3.63 Ethylene 30.38 28.17 30.20 27.71  27.74  26.94 Propane 19.81 25.60 24.07 0.40 0.43 0.36 Propylene 18.37 18.83 18.1314.76  14.48  12.04  i-butane 0.04 0.06 0.05 0.03 0.03 0.02 n-butane0.00 0.00 0.00 0.00 0.00 0.00 Propadiene 0.05 0.05 0.04 0.09 0.09 0.08Acetylene 0.04 0.04 0.05 0.12 0.10 0.10 t-2-butene 0.00 0.00 0.00 0.000.00 0.00 1-butene 0.23 0.22 0.19 0.45 0.43 0.44 i-butylene 0.81 0.970.97 1.27 1.02 1.04 c-2-butene 0.63 0.76 0.55 3.38 3.31 2.94 i-pentane0.19 0.18 0.16 0.02 0.02 0.03 n-pentane 0.01 0.01 0.04 1.27 1.12 2.081,3-butadiene 2.11 2.29 2.45 3.64 3.52 3.45 methyl acetylene 0.17 n/an/a 0.41 0.37 0.37 t-2-pentene 0.16 0.13 0.12 0.12 0.12 0.132-methyl-2-butene 0.03 0.03 0.03 0.05 0.06 0.09 1-pentene 0.02 0.02 0.020.08 0.10 0.12 c-2-pentene 0.11 0.10 0.09 0.08 0.09 0.11 pentadiene 10.00 0.00 0.00 0.05 0.08 0.14 pentadiene 2 0.01 0.03 0.02 0.23 0.36 0.53pentadiene 3 0.00 0.00 0.00 0.00 0.00 0.00 1,3-Cyclopentadiene 0.26 0.260.25 0.50 0.55 0.58 pentadiene 4 0.00 0.00 0.00 0.00 0.00 0.00pentadiene 5 0.09 0.08 0.08 0.00 0.00 0.12 CO₂ 0.00 0.00 0.00 0.02 0.000.00 CO 0.00 0.00 0.00 0.06 0.06 0.03 Hydrogen 1.21 1.12 1.24 0.96 0.950.95 Unidentified 0.00 0.00 0.00 20.04  19.77  19.63  Olefin/AromaticsRatio 18.48 24.43 23.07 9.22 10.46 8.67 Total Aromatics 2.88 2.13 2.305.69 4.97 5.62 Propylene +− Ethylene 48.75 47.00 48.33 42.47  42.22 38.98  Ethylene/Propylene Ratio 1.65 1.50 1.67 1.88 1.92 2.24 Carbonfrom Decoking, mg 96 44 32 90    71    23    *5% N₂ was also added tofacilitate steam generation. Analysis has been normalized to exclude it.**100% accountability based on actual reactor effluent gas flow rate andgas chromatography analysis and calculation to give theoretical mass ofunidentified products.

The cracking results showed the same general trends that were seen inthe other cases, such as r-propylene and r-ethylene yield and totalaromatics increasing with a lower steam to hydrocarbon ratio due to thelonger residence time in the reactor. These runs were made to determinethe amount of carbon generated when a r-pyoil was cracked with propaneor natural gasoline. These were short runs but they was sufficientlyaccurate to see trends in coking. Cracking propane produced the leastcoking. The carbon produced ranged from 16 to 51 mg at 0.2 or lesssteamlghydrocarbon ratio. Coking was the smallest at a 0.4steam/hydrocarbon ratio. In fact, only 1.5 mg of carbon was determinedafter decoking in Comp Ex 13. A much longer run time is needed toimprove accuracy. Since most commercial plants operate at a steam tohydrocarbon ratio of 0.3 or higher, the 51 mg obtained at 0.2 ratio maynot be unreasonable and may be considered a baseline for other feeds.For the r-pyoil/propane feed in Ex 53-55, increasing the ratio from 0.1to 0.2 to 0.4 decreased the amount of carbon obtained from 96 mg (Ex 53)to 32 mg (Ex 55). Even the 44 mg of carbon at a 0.2 ratio (Ex 54) wasnot unreasonable. Thus, using a 0.4 ratio for the combined r-pyoil andpropane feed inhibited coke formation similar to using a 0.2-0.4 ratiofor propane. Cracking r-pyoil with natural gasoline required a 0.7 ratio(Ex 58) to decrease the carbon obtained to the 20-50 mg range. At a 0.6ratio, (Ex 57) 71 mg of carbon was still obtained. Thus, operation of an80/20 mixture of natural gasoline and r-pyoil should use a ratio of 0.7or greater to provide runtimes typical for operation of propanecracking.

Increasing the steam to hydrocarbon ratio decreased the amount of cokeformed in cracking propane, propane and r-pyoil, and natural gasolineand r-pyoil. A higher ratio was required as a heavier feedstock wascracked. Thus, propane required the lowest ratio to obtain low cokeformation. Cracking propane and r-pyoil required a ratio of about 0.4. Arange of 0.4 to 0.6 would be adequate to allow typical commercialruntimes between decoking. For the natural gasoline and r-pyoil mixture,even a higher ratio was required. In this case, a ratio of 0.7 or aboveis needed. Thus, operating at a steam to hydrocarbon ratio of 0.7 to 0.9would be adequate to allow typical commercial runtimes between decoking.

Ex 59—Plant Test

About 13,000 gallons from tank 1012 of r-pyoil were used in the planttest as show in FIG. 12 . The furnace coil outlet temperature wascontrolled either by the testing coil (Coil-A 1034 a or Coil-B 1034 b)outlet temperature or by the propane coil (Coil C 1034 c, coil D 1034 dthrough F) outlet temperature, depending on the objective of the test.In FIG. 12 the steam cracking system with r-pyoil 1010; 1012 is ther-pyoil tank; 1020 is the r-pyoil tank pump; 1024 a and 1226 b are TLE(transfer line exchanger); 1030 a, b, c is the furnace convectionsection; 1034 a, b, c, d are the coils in furnace firebox (the radiantsection); 1050 is the r-pyoil transfer line; 1052 a, b are the r-pyoilfeed that is added into the system; 1054 a, b, c, d are the regularhydrocarbon feed; 1058 a, b, c, d—are dilution steam; 1060 a and 1060 bare cracked effluent. The furnace effluent is quenched, cooled toambient temperature and separated out condensed liquid, the gas portionis sampled and analyzed by gas chromatograph.

For the testing coils, propane flow 1054 a and 1054 b were controlledand measured independently. Steam flow 1058 a and 1058 b were eithercontrolled by Steam/HC ratio controller or in an AUTO mode at a constantflow, depending on the objective of the test. In the non-testing coils,the propane flow was controlled in AUTO mode and steam flow wascontrolled in a ratio controller at Steam/Propane=0.3.

r-pyoil was obtained from tank 1012 through r-pyoil flow meters and flowcontrol valves into propane vapor lines, from where r-pyoil flowed alongwith propane into the convection section of the furnace and further downinto the radiant section also called the firebox. FIG. 12 shows theprocess flow.

The r-pyoil properties are shown in and Table 15 and FIG. 23 . Ther-pyoil contained a small amount of aromatics, less than 8 wt. %, but alot of alkanes (more than 50%), thus making this material as a preferredfeedstock for steam cracking to light olefins. However, the r-pyoil hada wide distillation range, from initial boiling point of about 40° C. toan end point of about 400° C., as shown in Table 15 and FIGS. 24 and 25, covering a wide range of carbon numbers (C₄ to C₃₀ as shown in Table15). Another good characteristic of this r-pyoil is its low sulfurcontent of less than 100 ppm, but the r-pyoil had high nitrogen (327ppm) and chlorine (201 ppm) content. The composition of the r-pyoil bygas chromatography analysis is shown in Table 16.

TABLE 15 Properties of r-pyoil for plant test. Physical PropertiesDensity, 22.1° C., g/ml 0.768 Viscosity, 22.1 C., cP 1.26 InitialBoiling Point, ° C. 45 Flash Point, ° C. Below −1.1 Pour Point, ° C.−5.5 Impurities Nitrogen, ppmw 327 Sulfur, ppmw 74 Chlorine, ppmw 201Hydrocarbons, wt % Total Identified alkanes 58.8 Total IdentifiedAromatics 7.2 Total Identified Olefins 16.7 Total Identified Dienes 1.1Total Identified Hydrocarbons 83.5

TABLE 16 r-Pyoil composition. Component wt % Propane 0.17 1,3-Butadiene0.97 Pentene 0.40 Pentane 3.13 2-methyl-Pentene 2.14 2-methyl-Pentane2.46 Hexane 1.83 2,4-dimethylpentene 0.20 Benzene 0.175-methyl-1,3-cyclopentadiene 0.17 Heptene 1.15 Heptane 2.87 Toluene 1.074-methylheptane 1.65 Octene 1.51 Octane 2.77 2,4-dimethylheptene 1.522,4-dimethylheptane 3.98 Ethylbenzene 3.07 m,p-xylene 0.66 Styrene 1.11Mol. Weight = 140 1.73 Nonane 2.81 Cumene 0.96 Decene/methylstyrene 1.16Decane 3.16 Indene 0.20 Indane 0.26 C11-Alkene 1.31 C11-Alkane 3.29Napthanlene 0.00 C12-Alkene 1.29 C12-Alkane 3.21 C13-Alkene 1.19C13-Alkane 2.91 2-methylnapthalene 0.62 C14-Alkene 0.83 C14-Alkane 3.02acenapthalene 0.19 C15-alkene 0.86 C15-alkane 3.00 C16-Alkene 0.58C16-Alkane 2.66 C17-Alkene 0.46 C17-Alkane 2.42 C18-Alkene 0.32C18-Alkane 2.10 C19-Alkene 0.37 C19-Alkane 1.81 C20-Alkene 0.25C20-Alkane 1.53 C21-Alkene 0.00 C21-Alkane 1.28 C22-Alkane 1.10C23-Alkane 0.87 C24-Alkane 0.72 C25-Alkane 0.57 C26-Alkane 0.47C27-Alkane 0.36 c28-Alkane 0.28 c29-Alkane 0.22 C30-Alkane 0.17 TotalIdentified 83.5%

Before the plant test started, eight (8) furnace conditions (morespecifically speaking, eight conditions on the testing coils) werechosen. These included r-pyoil content, coil outlet temperature, totalhydrocarbon feeding rate, and the ratio of steam to total hydrocarbon.The test plan, objective and furnace control strategy are shown in Table17. “Float Mode” means the testing coil outlet temperature is notcontrolling the furnace fuel supply. The furnace fuel supply iscontrolled by the non-testing coil outlet temperature, or the coils thatdo not contain r-pyoil.

TABLE 17 Plan for the plant test of r-pyoil co-cracking with propane.Pyoil TOTAL, Pyoil/coil, Pyoil/coil, Stm/HC Propane/coil, Condition COT,° F. w % Py/C₃H₈ KLB/HR GPM lb/hr ratio klb/hr Base-line 1500 0 0.0006.0 0.00 0 0.3 6.00 1A Float Mode 5 0.053 6.0 0.79 300 0.3 5.70 1B FloatMode 10 0.111 6.0 1.58 600 0.3 5.40 1C & 2A Float Mode 15 0.176 6.0 2.36900 0.3 5.10 2B Lower by at 15 0.176 6.0 2.36 900 0.3 5.10 least 10 F.than the baseline 3A & 2C 1500 15 0.176 6.0 2.36 900 0.3 5.10 3B 1500 150.176 6.9 2.72 1035 0.3 5.87 4A 1500 15 0.176 6.0 2.36 900 0.4 5.10 4B1500 15 0.176 6.0 2.36 900 0.5 5.10 5A Float Mode 4.8 0.050 6.3 0.79 3000.3 6.00 5B At 2B COT 4.8 0.050 6.3 0.79 302 0.3 6.00Effect of Addition of r-Pyoil

The results of r-Pyoil addition can be observed differently depending onhow propane flow, steam/HC ratio and furnace are controlled.Temperatures at crossover and coil outlet changed differently dependingon how propane flow and steam flow are maintained and how the furnace(the fuel supply to the firebox) was controlled. There were six coils inthe testing furnace. There were several ways to control the furnacetemperature via the fuel supply to the firebox. One of them was tocontrol the furnace temperature by an individual coil outlettemperature, which was used in the test. Both a testing coil and anon-testing coil were used to control the furnace temperature fordifferent test conditions.

Ex 59.1—at Fixed Propane Flow, Steam/HC Ratio and Furnace Fuel Supply(Condition 5A)

In order to check the r-pyoil 1052 a addition effect, propane flow andsteam/HC ratio were held constant, and furnace temperature was set tocontrol by a non-testing coil (Coil-C) outlet temperature. Then r-pyoil1052 a, in liquid form, without preheating, was added into the propaneline at about 5% by weight.

Temperature changes: After the r-pyoil 1052 a addition, the crossovertemperature dropped about 10° F. for A and B coil, COT dropped by about7° F. as shown in Table 18. There are two reasons that the crossover andCOT temperature dropped. One, there was more total flow in the testingcoils due to r-pyoil 1052 a addition, and two, r-pyoil 1052 aevaporation from liquid to vapor in the coils at the convection sectionneeded more heat thus dropping the temperature down. With a lower coilinlet temperature at the radiant section, the COT also dropped. The TLEexit temperature went up due to a higher total mass flow through the TLEon the process side.

Cracked gas composition change: As can be seen from the results in Table18, methane and r-ethylene decreased by about 1.7 and 2.1 percentagepoints, respectively, while r-propylene and propane increased by 0.5 and3.0 percentage points, respectively. The propylene concentrationincreased as did the propylene:ethylene ratio relative to the baselineof no pyoil addition. This was the case even though the propaneconcentration also increased. Others did not change much. The change inr-ethylene and methane was due to the lower propane conversion at thehigher flow rate, which was shown by a much higher propane content inthe cracked gas.

TABLE 18 Changes When Hydrocarbon Mass Flow Increases By Adding r-pyoilTo Propane At 5% At Constant Propane Flow, Steam/HC Ratio And FireboxCondition. Base-line Base-line 5A Add in Pyoil A&B Propane flow, klb/hr11.87 11.86 11.85 A&B Pyoil How, lb/hr 0 0 593 A&B Steam flow, lb/hr3562 3556 3737 A&B total HC flow, klb/hr 11.87 11.86 12.44 Pyoil/(poil +propane), % 0.0 0.0 4.8 Steam/HC, ratio 030 0.30 0.30 A&B Crossover T, F1092 1091 1081 A&B COT, F 1499 1499 1492 A&B TLE Exit T, F 691 691 698A&B TLE Inlet, PSIG 10.0 10.0 10.0 A&B TLE Exit T, PSIG 9.0 9.0 9.0Cracked Gas Product wt % wt % wt % Hydrogen 1.26 1.39 1.29 Methane 18.8318.89 17.15 Ethane 4.57 4.54 4.38 Ethylene 31.25 31.11 28.94 Acetylene0.04 0.04 0.04 Propane 20.13 21.25 24.15 Propylene 17.60 17.88 18.36MAPD 0.26 0.25 0.25 Butanes 0.11 0.12 0.15 Butadiene 1.73 1.67 1.65Butenes + CPD 1.41 1.41 1.62 Other C5s 0.42 0.37 0.40 C6s+ 1.34 0.931.55 CO2 0.046 0.022 0.007 CO 1.001 0.134 0.061 Aver. M.W. 24.5 24.225.1

In order to check how the temperatures and crack gas composition changedwhen the total mass of hydrocarbons to the coil was held constant whilethe percent of r-pyoil 1052 a in the coil varied, steam flow to thetesting coil was held constant in AUTO mode, and the furnace was set tocontrol by a non-testing coil (Coil-C) outlet temp to allow the testingcoils to be in Float Mode. The r-pyoil 1052 a, in liquid form, withoutpreheating, was added into propane line at about 5, 10 and 15% byweight, respectively. When r-pyoil 1052 a flow was increased, propaneflow was decreased accordingly to maintain the same total mass flow ofhydrocarbon to the coil. Steam/HC ratio was maintained at 0.30 by aconstant steam flow.

Temperature Change: As the r-pyoil 1052 a content increased to 15%,crossover temperature dropped modestly by about 5° F., COT increasedgreatly by about 15° F., and TLE exit temperature just slightlyincreased by about 3° F., as shown in Table 19.

Cracked gas composition change: As r-pyoil 1052 a content in the feedincreased to 15%, methane, ethane, r-ethylene, r-butadiene and benzenein cracked gas all went up by about 0.5, 0.2, 2.0, 0.5, and 0.6percentage points, respectively. r-Ethylene/r-propylene ratio went up.Propane dropped significantly by about 3.0 percentage points, butr-propylene did not change much, as shown in Table 19A. These resultsshowed the propane conversion increased. The increased propaneconversion was due to the higher COT. When the total hydrocarbon feed tocoil, steam/HC ratio and furnace fuel supply are held constant, the COTshould go down when crossover temperature drops. However, what was seenin this test was opposite. The crossover temperature declined but COTwent up, as shown in Table 19a. This indicates that r-pyoil 1052 acracking does not need as much heat as propane cracking on the same massbasis.

TABLE 19A Variation of R-pyoil content and its effect on cracked gas andtemperatures (Steam/HC ratio and furnace firebox were held constant).Base- Base- 1A, 5% 1A, 5% 1B, 10% 1B, 10% 1C, 15% 1C, 15% line linePyoil Pyoil Pyoil Pyoil Pyoil pyoil A&B Propane flow, klb/hr 11.87 11.8611.25 11.25 10.66 10.68 10.06 10.07 A&B Pyoil Flow, lb/hr 0 0 537 5361074 1074 1776 1778 A&B Steam flow, lb/hr 3562 3556 3544 3543 3523 35233562 3560 A&B total HC flow, klb/hr 11.87 11.86 11.79 11.78 11.74 11.7511.84 11.85 Pyoil/(poil + propane), % 0.0 0.0 4.6 4.6 9.2 9.1 15.0 15.0Steam/HC, ratio 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 A&B Crossover T,F 1092 1091 1092 1092 1090 1090 1088 1087 A&B COT, F 1499 1499 1503 15031509 1509 1514 1514 A&B TLE Exit T, F 691 691 692 692 692 692 693 693A&B TLE Inlet, PSIG 10.0 10.0 10.5 10.5 10.0 10.0 10.0 10.0 A&B TLE ExitT, PSIG 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 Cracked Gas Product wt % wt % wt% wt % wt % wt % wt % wt % Hydrogen 1.26 1.39 1.40 1.32 1.33 1.28 1.311.18 Methane 18.83 18.89 18.96 18.74 19.31 19.08 19.61 19.16 Ethane 4.574.54 4.59 4.69 4.70 4.81 4.67 4.85 Ethylene 31.25 31.11 31.52 31.6232.50 32.63 33.06 33.15 Acetylene 0.04 0.04 0.04 0.04 0.05 0.05 0.050.05 Propane 20.13 21.25 20.00 19.95 18.58 18.65 16.97 17.54 Propylene17.60 17.88 17.85 17.86 17.79 17.85 17.58 17.81 MAPD 0.26 0.25 0.27 0.270.29 0.29 0.30 0.30 Butanes 0.11 0.12 0.11 0.11 0.10 0.10 0.10 0.10Butadiene 1.73 1.67 1.86 1.86 2.04 2.03 2.23 2.17 Butenes + CPD 1.411.41 1.52 1.52 1.59 1.57 1.67 1.65 Other C5s 0.42 0.37 0.38 0.38 0.380.37 0.40 0.39 C6s+ 1.34 0.93 1.37 1.50 1.24 1.21 1.95 1.56 CO2 0.0460.022 0.012 0.016 0.011 0.011 0.007 0.008 CO 1.001 0.134 0.107 0.1070.085 0.088 0.086 0.084 Aver. M.W. 24.5 24.2 24.2 24.4 24.2 24.4 24.224.6 Ex 59.3 At constant COT and steam/HC ratio (Conditions 2B, & 5B).

In the previous test and comparison, effect of r-pyoil 1052 a additionon cracked gas composition was influenced not only by r-pyoil 1052 acontent but also by the change of COT because when r-pyoil 1052 a wasadded, COT changed accordingly (it was set to Float Mode). In thiscomparison test, COT was held constant. The test conditions and crackedgas composition are listed in Table 19B. By comparing the data in Table19B, the same trend in cracked gas composition was found as in the caseEx 59.2. When r-pyoil 1052 a content in the hydrocarbon feed wasincreased, methane, ethane, r-ethylene, r-butadiene in cracked gas wentup, but propane dropped significantly while r-propylene did not changemuch.

TABLE 19B Changing r-Pyoil 1052a content in HC feed at constant coiloutlet temperature. 5B, Pyoil 2B, 15% 2B, 15% 5%@low T Pyoil Pyoil A&BPropane flow, klb/hr 11.85 10.07 10.07 A&B Pyoil Flow, lb/hr 601 17781777 A&B Steam flow, lb/hr 3738 3560 3559 A& B total HC flow, klb/hr12.45 11.85 11.85 Pyoil/(poil + propane), % 4.8 15.0 15.0 Steam/HC,ratio 0.30 0.30 0.30 A&B Crossover T, F 1062 1055 1059 A&B COT, F 14781479 1479 A&B TLE Exit T, F 697 688 688 A&B TLE Inlet, PSIG 10.0 10.010.0 A&B TLE Exit T, PSIG 9.0 9.0 9.0 Cracked Gas Product wt % wt % wt %Hydrogen 1.20 1.12 1.13 Methane 16.07 16.60 16.23 Ethane 4.28 4.81 4.65Ethylene 27.37 29.33 28.51 Acetylene 0.03 0.04 0.04 Propane 27.33 24.0125.51 Propylene 18.57 18.45 18.59 MAPD 0.23 0.27 0.25 Butanes 0.17 0.140.16 Butadiene 1.50 1.94 1.76 Butenes + CPD 1.63 1.65 1.73 Other C5s0.40 0.35 0.35 C6s+ 1.17 1.21 1.03 CO2 0.007 0.010 0.007 CO 0.047 0.0650.054 Aver. M.W. 25.8 25.7 25.9 C2H4/C3H6, wt/wt 1.47 1.59 1.53

r-Pyoil 1052 a in the hydrocarbon feed was held constant at 15% for 2B,and 2C. r-pyoil for 5A and 5B were reduced to 4.8%. The totalhydrocarbon mass flow and steam to HC ratio were both held constant.

On cracked gas composition. When COT increased from 1479° F. to 1514° F.(by 35° F.), r-ethylene and r-butadiene in the cracked gas went up byabout 4.0 and 0.4 percentage points, respectively, and r-propylene wentdown by about 0.8 percentage points, as shown in Table 20.

When r-pyoil 1052 a content in the hydrocarbon feed was reduced to 4.8%,the COT effect on the cracked gas composition followed the same trend asthat with 15% r-Pyoil 1052 a.

TABLE 20 Effect of COT on cracked gas composition. (Steam/HC ratio,R-pyoil 1052a content in the feed and total hydrocarbon mass flow wereall held constant) 1C, 15% 1C, 15% 2B, 15% 2B, 15% 2C, 15% 2C, 15% 5A,Add in 5B, Pyoil Pyoil pyoil Pyoil Pyoil Pyoil Pyoil Pyoil 5% to C₃H₈5%@low T A&E Propane flow, klb/hr 10.06 10.07 10.07 10.07 10.07 10.0611.85 11.85 A&B Pyoil Flow, lb/hr 1776 1778 1778 1777 1777 1776 593 601A&B Steam flow, lb/hr 3562 3560 3560 3559 3560 3559 3737 3738 A&B totalHC flow, klb/hr 11.84 11.85 11.85 11.85 11.84 11.84 12.44 12.45Pyoil/(poil + propane), % 15.0 15.0 15.0 15.0 15.0 15.0 4.8 4.8Steam/HC, ratio 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 A&B Crossover T,F 1088 1087 1055 1059 1075 1076 1081 1062 A&B COT, F 1514 1514 1479 14791497 1497 1492 1478 A&B TLE Exit T, F 693 693 688 688 690 691 698 697A&B TLE Inlet, PSIG 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 A&B TLE ExitT, PSIG 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 Cracked Gas Product wt % wt % wt% wt % wt % wt % wt % wt % Hydrogen 1.31 1.18 1.12 1.13 1.26 1.25 1.291.20 Methane 19.61 19.16 16.60 16.23 18.06 17.87 17.15 16.07 Ethane 4.674.85 4.81 4.65 4.72 4.75 4.38 4.28 Ethylene 33.06 33.15 29.33 28.5131.03 30.73 28.94 27.37 Acetylene 0.05 0.05 0.04 0.04 0.04 0.04 0.040.03 Propane 16.97 17.54 24.01 25.51 21.17 21.10 24.15 27.33 Propylene17.58 17.81 18.45 18.59 18.29 18.30 18.36 18.57 MAPD 0.30 0.30 0.27 0.250.27 0.28 0.25 0.23 Butanes 0.10 0.10 0.14 0.16 0.13 0.13 0.15 0.17Butadiene 2.23 2.17 1.94 1.76 1.87 1.99 1.65 1.50 Butenes + CPD 1.671.65 1.65 1.73 1.71 1.77 1.62 1.63 Other C5s 0.40 0.39 0.35 0.35 0.370.40 0.40 0.40 C6s+ 1.95 1.56 1.21 1.03 1.00 1.30 1.55 1.17 CO2 0.0070.008 0.010 0.007 0.009 0.009 0.007 0.007 CO 0.086 0.084 0.065 0.0540.070 0.072 0.061 0.047 Aver. M.W. 24.2 24.6 25.7 25.9 24.8 24.9 25.125.8 Ex 59.5 Effect of steam/HC ratio (Conditions 4A & 4B).

Steam/HC ratio effect is listed in Table 21A. In this test, r-pyoil 1052a content in the feed was held constant at 15%. COT in the testing coilswas held constant in SET mode, while the COTs at non-testing coils wereallowed to float. Total hydrocarbon mass flow to each coil was heldconstant.

On temperature. When steam/HC ratio was increased from 0.3 to 0.5, thecrossover temperature dropped by about 17° F. since the total flow inthe coils in the convection section increased due to more dilutionsteam, even though the COT of the testing coil was held constant. Due tothe same reason, TLE exit temperature went up by about 13 F.

On cracked gas composition. In the cracked gas, methane and r-ethylenewere reduced by 1.6 and 1.4 percentage points, respectively, and propanewas increased by 3.7 percentage points. The increased propane in thecracked gas indicated propane conversion dropped. This was due to,firstly, a shorter residence time, since in the 4B condition, the totalmoles (including steam) going into the coils was about 1.3 times of thatin 2° C. condition (assuming the average molecular weight of r-pyoil1052 a was 160), and secondly, to the lower crossover temperature whichwas the inlet temperature for the radiant coil, making the averagecracking temperature lower.

TABLE 21A Effect of steam/HC ratio. (r-Pyoil in the HC feed at 15%,total hydrocarbon mass flow and COT were held constant). 2C, 15% 2C, 15%4A, Stm 4B, Stm Pyoil Pyoil ratio 0.4 ratio 0.5 A&B Propane flow, 10.0710.06 10.08 10.08 klb/hr A&B Pyoil Flow, lb/hr 1777 1776 1778 1778 A&BSteam flow, lb/hr 3560 3559 4748 5933 A&B total HC flow, 11.84 11.8411.85 11.85 klb/hr Pyoil/(poil + propane), % 15.0 15.0 15.0 15.0Steam/HC, ratio 0.30 0.30 0.40 0.50 A&B Crossover T, F 1075 1076 10631058 A&B COT, F 1497 1497 1498 1498 A&B TLE Exit T, F 690 691 698 703A&B Feed Pres, PSIG 69.5 69.5 67.0 67.0 A&B TLE Inlet, PSIG 10.0 10.010.0 11.0 A&B TLE Exit T, PSIG 9.0 9.0 9.0 9.0 Cracked Gas Product wt %wt % wt % wt % Hydrogen 1.26 1.25 0.87 1.12 Methane 18.06 17.87 16.3016.18 Ethane 4.72 4.75 4.55 4.38 Ethylene 31.03 30.73 29.92 29.52Acetylene 0.04 0.04 0.05 0.05 Propane 21.17 21.10 23.40 24.88 Propylene18.29 18.30 18.67 18.49 MAPD 0.27 0.28 0.29 0.28 Butanes 0.13 0.13 0.150.16 Butadiene 1.87 1.99 2.01 1.85 Butenes + CPD 1.71 1.77 1.89 1.81Other C5s 0.37 0.40 0.43 0.37 C6s+ 1.00 1.30 1.38 0.84 CO2 0.009 0.0090.026 0.008 CO 0.070 0.072 0.070 0.061

On cracked gas composition. In the cracked gas, methane and r-ethylenewere reduced by 1.6 and 1.4 percentage points, respectively, and propanewas increased

Renormalized cracked gas composition. In order to see what the lighterproduct composition could be if ethane and propane in the cracked gaswould be recycled, the cracked gas composition in Table 21A wasrenormalized by taking off propane or ethane+propane, respectively. Theresulting composition is listed in Table 21B. It can be seen, olefin(r-ethylene+r-propylene) content went up with steam/HC ratio.

TABLE 21B Renormalized cracked gas composition. (R-pyoil in the HC feedat 15%, total hydrocarbon mass flow and COT were held constant). 2C, 15%4A, Stm 4B, Stm Pyoil ratio 0.4 ratio 0.5 A&B Propane, flow, klb/hr10.07 10.08 10.08 Pyoil/(poil + propane), % 15.0 15.0 15.0 Steam/HC,ratio 0.30 0.40 0.50 A&B Crossover T, F 1075 1063 1058 A&B COT, F 14971498 1498 Renorm. w/o Propane wt % wt % wt % Hydrogen 1.60 1.14 1.49Methane 22.91 21.28 21.54 Ethane 5.99 5.94 5.83 Ethylene 39.36 39.0639.29 Acetylene 0.05 0.06 0.06 Propylene 23.21 24.37 24.62 MAPD 0.340.38 0.38 Butanes 0.17 0.20 0.21 Butadiene 2.37 2.63 2.46 Butenes + CPD2.16 2.47 2.41 Other C5s 0.46 0.56 0.50 C6s+ 1.27 1.80 1.12 CO2 0.0110.033 0.010 CO 0.089 0.091 0.081 C2H4 + C3H6 62.57 63.43 63.91 Renorm.w/o C2H6 + C3H8 wt % wt % wt % Hydrogen 1.70 1.21 1.58 Methane 24.3722.62 22.87 Ethylene 41.87 41.52 41.73 Acetylene 0.06 0.06 0.06Propylene 24.69 25.91 26.15 MAPD 0.36 0.40 0.40 Butanes 0.18 0.21 0.22Butadiene 2.52 2.79 2.61 Butenes + CPD 2.30 2.62 2.55 Other C5s 0.490.60 0.53 C6s+ 1.35 1.91 1.19 CO2 0.012 0.035 0.011 CO 0.094 0.097 0.086C2H4 + C3H6 66.55 67.43 67.87

Effect of total hydrocarbon feed flow (Conditions 2C & 3B) An increasein total hydrocarbon flow to the coil means a higher throughput but ashorter residence time, which reduces conversion. With r-pyoil 1052 a at15% in the HC feed, a 10% increase of the total HC feed brought about aslight increase in the propylene:ethylene ratio along with an increasein the concentration of propane without a change in ethane, when COT washeld constant. Other changes were seen on methane and r-ethylene. Eachdropped about 0.5˜0.8 percentage points. The results are listed in Table22.

TABLE 22 Comparison of more feed to coil (Steam/HC ratio = 0.3, COT isheld constant at 1497F). 2C, 15% 2C, 15% 3B, 10% 3B, 10% Pyoil Pyoilmore FD more FD A&B Propane flow, 10.07 10.06 11.09 11.09 klb/hr A&BPyoil Flow, lb/hr 1777 1776 1956 1957 A&B Steam flow, lb/hr 3560 35593916 3916 A&B total HC flow, 11.84 11.84 13.04 13.05 klb/hrPyoil/(poil + propane), % 15.0 15.0 15.0 15.0 Steam/HC, ratio 0.30 0.300.30 0.30 A&B Crossover T, F 1075 1076 1066 1065 A&B COT, F 1497 14971497 1497 A&B TLE Exit T, F 690 691 698 699 A&B TLE Inlet, PSIG 10.010.0 10.3 10.3 A&B TLE Exit T, PSIG 9.0 9.0 9.0 9.0 Cracked Gas Productwt % wt % wt % wt % Hydrogen 1.26 1.25 1.19 1.24 Methane 18.06 17.8717.23 17.31 Ethane 4.72 4.75 4.76 4.79 Ethylene 31.03 30.73 30.02 29.95Acetylene 0.04 0.04 0.04 0.04 Propane 21.17 21.10 22.51 22.31 Propylene18.29 18.30 18.44 18.28 MAPD 0.27 0.28 0.28 0.28 Butanes 0.13 0.13 0.150.14 Butadiene 1.87 1.99 1.93 1.95 Butenes + CPD 1.71 1.77 1.82 1.82Other C5s 0.37 0.40 0.41 0.42 C6s+ 1.00 1.30 1.15 1.39 CO2 0.009 0.0090.009 0.008 CO 0.070 0.072 0.065 0.066

r-pyoil 1052 a is successfully co-cracked with propane in the same coilon a commercial scale furnace.

Ex 60 An average 24 hour feed to an ethylene fractionator over 84 dayswas determined to be 123.4 klb/hr (min 117.1 and max of 127.3). Thereflux ratio was determined as a function of ethylene concentration ofthe feedstock to the ethylene fractionation column. The results areshown in FIG. 26 . As can be seen, the reflux ratio decreases as theconcentration of ethylene in the feedstock increases.

1-50. (canceled)
 51. A method of processing a pyrolysis recycle contentmixed ester composition derived directly or indirectly from thepyrolysis of a recycled waste (“pr-ROH”), said method comprising feedingsaid pr-ROH to a reactor in which a mixed ester is made.
 52. A method ofmaking recycle content mixed ester composition (“r-EC”), said methodcomprising reacting an alcohol composition at least a portion of whichis derived directly or indirectly from pyrolyzing a recycled waste(“pr-ROH”) with an acid to produce a mixed ester effluent comprisingr-EC.
 53. A recycle content mixed ester (“r-EC”) having a monomerderived from a recycle content alcohol composition (“r-ROH”).
 54. Arecycle content mixed ester composition (“r-EC”) obtained claim
 51. 55.A recycle content mixed ester composition (“r-EC”) obtained by claim 52.56. The method of claim 51, wherein said r-olefin, r-AD, r-ROH, or r-ECis derived directly or indirectly from pyrolyzing recycle waste, oroptionally from cracking r-pyoil or obtained from r-pygas.
 57. Themethod of claim 51, wherein said r-olefin, r-AD, r-ROH, or r-EC isderived directly or indirectly from cracking r-pyoil in a gas furnace.58. The method of claim 51, wherein the EC composition has associatedwith it, or contains, or is labelled, advertised, or certified ascontaining recycle content in an amount of at least 0.01 wt. %, based onthe weight of the EC composition.
 59. The method 51, wherein a recyclecontent value is applied to the EC through deducting the value from arecycle inventory or reacting a r-ROH to make a r-EC.
 60. The methodclaim 52, wherein the method for apportioning the recycle content amongproducts made by an EC manufacturer or the products made by any oneentity or a combinations of entities among the Family of Entities ofwhich the EC manufacturer is a part, is a symmetric distribution ofrecycle content values among their product(s), and optionally at leastone of the products is EC.
 61. The method of claim 51, wherein themethod for apportioning the recycle content among products made by an ECmanufacturer or the products made by any one entity or a combinations ofentities among the Family of Entities of which the EC manufacturer is apart, is an asymmetric distribution of recycle content values amongtheir product(s), and optionally at least one of the products is EC. 62.The method of claim 51, wherein the ROH supplier transfers a recyclecontent allotment to the EC manufacturer and a supply of ROH to the ECmanufacturer.
 63. The method of claim 51, wherein the recycle contentallotment is not associated with the ROH supplied.
 64. The method ofclaim 51 wherein the ROH supplier transfers a recycle content allotmentto the EC manufacturer and a supply of ROH to the EC manufacturer, andthe recycle content allotment is associated with ROH made by thesupplier.
 65. The method of claim 52 wherein the ROH supplier transfersa recycle content allotment to the EC manufacturer and a supply of ROHto the EC manufacturer, and the recycle content allotment is associatedwith ROH made by the supplier
 66. The method of claim 51, wherein theROH supplied is r-ROH and at least a portion of the recycle contentallotment being transferred is the recycle content in the r-ROHsupplied.
 67. The method of claim 51, wherein the EC manufacturerdeposits the allotment into a recycle inventory.
 68. The method of claim51, wherein the EC manufacturer, or any person or entity among itsFamily of Entities: a. deposits an allotment into a recycle inventoryand stores it; or b. deposits an allotment into a recycle inventory andapplies a recycle content value from the recycle inventory to productsother than EC made by the EC manufacturer, or c. sells or transfers anallotment from the recycle inventory into which the allotment obtainedas noted above was deposited, or d. applies a recycle content value toEC drawn from the recycle inventory.
 69. The method of claim 51, whereinthe recycle content value applied to EC drawn from a recycle inventoryis derived directly or indirectly from the pyrolysis of recycled waste.70. The method of claim 52, wherein the recycle content value applied toEC drawn from a recycle inventory is derived directly or indirectly fromthe pyrolysis of recycled waste.